Computationalscreening of novel thiamine-catalyzed decarboxylation reactions of 2-keto acids
Rajeev S. Assary and Linda J. Broadbelt*
Department of Chemical and Biological Engineering,
Northwestern University, Evanston, Illinois 60208
Corresponding author: Linda J. Broadbelt
Phone: (847) 491-5351; email:
Molecular geometries (B3LYP/6-31+G*)
The intermediates/molecules in the thiamine catalyzed decarboxylation mechanism explained in this paper listed down and their optimized Cartesian coordinates are given.
Step1. Isolated thiamine and ketoacid (A)
Step2: Transition state (TS1) of carbon-carbon bond formation
Step3: Initial complex (C)
Step4: Proton transfer transition state (TS2, D)
Step5: Tetrahedral intermediate, LThDP analogue (E)
Step6: Transition state (TS3) of carbon-carbon bond breaking (F)
Step 7: Enamine/carbanion formation (G)
optimized structure of Thiamine diphosphate model ( ThDP)
33
scf done: -1084.112603
N -26.939420 -64.698994 22.411480
C -25.690773 -65.025750 22.784570
C -24.909601 -63.997611 23.559034
N -25.069152 -66.178487 22.512006
C -25.731574 -67.105420 21.792976
N -25.099224 -68.288323 21.576242
C -27.058166 -66.858946 21.332451
C -27.589547 -65.631233 21.698320
C -27.869926 -67.890086 20.590251
N -27.403087 -68.164113 19.203853
C -26.476134 -69.125852 19.021144
S -26.145571 -69.153945 17.329492
C -27.274986 -67.860914 16.930869
C -27.867684 -67.435428 18.080346
C -28.899894 -66.357412 18.231784
C -27.464886 -67.372879 15.520786
C -26.290039 -66.525729 14.995850
H -24.268780 -64.480597 24.302233
H -24.257698 -63.434488 22.877794
H -25.586817 -63.290104 24.043328
H -24.125454 -68.320973 21.851621
H -27.831569 -68.855513 21.102900
H -28.917073 -67.579793 20.546998
H -29.118189 -65.904132 17.261990
H -29.845160 -66.746790 18.631364
H -28.558059 -65.558780 18.899845
H -27.613577 -68.235255 14.857447
H -28.390004 -66.786890 15.463587
H -26.139504 -65.635216 15.616549
H -25.355547 -67.097894 14.999345
H -25.393262 -68.890315 20.799048
H -28.612429 -65.379254 21.414147
H -26.483113 -66.199181 13.967248
pyruvic acid
10
scf done: -342.423425
C 1.596976 -1.028049 0.337423
C 0.675658 -0.099867 -0.392186
O 1.029813 0.810625 -1.122657
C -0.850938 -0.313349 -0.204478
O -1.312438 -1.183135 0.494860
O -1.588839 0.563439 -0.895820
H 1.390880 -2.064382 0.043976
H 2.634925 -0.769213 0.121077
H 1.404336 -0.973370 1.415559
H -0.967682 1.154834 -1.374616
pyruvic acid: TS1 (B)
43
scf done: -1426.529826
C -3.007260 -0.089614 -1.403638
C -1.903333 -0.551564 -0.693954
C -2.205634 -1.113216 0.577719
N -3.462863 -1.070497 1.067695
C -4.425112 -0.545206 0.306417
N -4.263148 -0.073236 -0.943553
C -0.518705 -0.502332 -1.294275
N 0.417774 0.476311 -0.662682
C 0.252941 1.881422 -0.771568
C 1.257449 2.554083 -0.143106
S 2.380255 1.393698 0.545942
C 1.500080 0.028921 -0.006270
C -0.888285 2.486835 -1.532739
C 2.129430 -2.190462 0.526205
C 3.252248 -2.085699 -0.530435
O 4.330472 -1.572861 -0.338748
C 1.459308 4.036697 0.016618
C 0.957009 4.582999 1.366879
N -1.271115 -1.694076 1.379256
C -5.815516 -0.489561 0.879710
O 1.148113 -2.901273 0.225677
C 2.508241 -1.901127 1.956749
O 2.912151 -2.679867 -1.687749
H -6.510573 -1.039929 0.235211
H -5.834898 -0.914630 1.885182
H -6.166963 0.548430 0.914965
H -1.660034 -2.177735 2.180301
H -0.012669 -1.466037 -1.218900
H -0.590269 -0.251838 -2.357775
H -0.725647 3.560642 -1.652555
H -0.981274 2.057566 -2.536992
H -1.846634 2.348132 -1.022205
H 2.525794 4.269104 -0.095920
H 0.949513 4.559795 -0.801234
H -0.117268 4.404898 1.488631
H 1.473973 4.102813 2.205189
H -0.433678 -2.120877 0.978926
H -2.870835 0.295331 -2.414963
H 1.135584 5.662517 1.431908
H 2.028678 -3.083835 -1.529118
H 2.931821 -2.826349 2.373142
H 3.266549 -1.120949 2.030690
H 1.624348 -1.634672 2.540450
pyruvic acid: initial complex (C)
43
scf done: -1426.551962
C 1.471510 0.143630 0.075492
N 0.384615 0.520765 -0.613908
C 0.189144 1.915266 -0.689734
C 1.151676 2.614072 -0.021271
S 2.299216 1.512905 0.688275
C -0.545374 -0.450993 -1.300537
C -1.937010 -0.481897 -0.724857
C -3.032899 -0.092128 -1.485562
N -4.301879 -0.099777 -1.061737
C -4.481332 -0.516972 0.206739
N -3.524670 -0.953952 1.026643
C -2.248246 -0.978707 0.576951
N -1.309154 -1.461008 1.421954
C -5.893354 -0.506645 0.728698
C -0.951320 2.508300 -1.460323
C 1.291669 4.100169 0.176451
C 0.651391 4.608501 1.482727
C 2.014801 -1.284743 0.279448
C 2.855210 -1.345562 1.582598
C 3.023271 -1.533549 -0.930199
O 2.726266 -2.687110 -1.511229
O 1.050391 -2.245436 0.241482
O 3.931312 -0.792922 -1.247069
H -6.506665 -1.216743 0.160675
H -5.915369 -0.779395 1.785760
H -6.341542 0.483664 0.590701
H -1.677200 -1.885538 2.264900
H -0.052731 -1.419626 -1.206040
H -0.574274 -0.156884 -2.353568
H -0.800991 3.584939 -1.564527
H -1.022807 2.087561 -2.468703
H -1.912360 2.346638 -0.963265
H 2.355604 4.366493 0.161409
H 0.841713 4.616197 -0.679134
H -0.421695 4.389861 1.508125
H 1.110946 4.139044 2.359620
H -0.398610 -1.816065 1.061642
H -2.880014 0.250253 -2.510509
H 0.782771 5.692669 1.571332
H 1.910752 -2.976825 -0.972455
H 3.224691 -2.370121 1.681570
H 3.717720 -0.669178 1.578228
H 2.215958 -1.128418 2.444878
pyruvic Acid: transition state 2 (TS2, D)
43
scf done: -1426.549349
C 0.190741 1.902749 -0.636005
N 0.395791 0.510095 -0.555435
C 1.485832 0.143614 0.137583
S 2.301702 1.521704 0.747748
C 1.146742 2.610858 0.031237
C -0.513853 -0.466764 -1.254412
C -1.922236 -0.496896 -0.717922
C -2.272319 -0.948265 0.588565
N -3.561088 -0.919006 0.997112
C -4.495118 -0.519469 0.132615
N -4.277101 -0.145530 -1.143131
C -2.996050 -0.142337 -1.526762
N -1.358127 -1.388904 1.485623
C -5.922719 -0.502227 0.608897
C 2.060198 -1.250044 0.320849
C 2.848444 -1.621271 -1.039436
O 2.367210 -2.755497 -1.445957
C 1.277437 4.098391 0.223514
C 0.634648 4.607925 1.528059
C -0.951333 2.485746 -1.411889
O 1.088918 -2.233206 0.433974
C 3.068075 -1.295428 1.485471
O 3.724568 -0.919070 -1.515868
H -6.516061 -1.225285 0.036272
H -5.977950 -0.752113 1.670321
H -6.368162 0.483912 0.435966
H -1.751280 -1.789172 2.329012
H -0.028225 -1.434778 -1.158606
H -0.517175 -0.182924 -2.310795
H -0.805785 3.562451 -1.521655
H -1.018497 2.059462 -2.418115
H -1.912698 2.322427 -0.916049
H 2.339724 4.371153 0.206602
H 0.824127 4.608166 -0.633937
H -0.437190 4.383355 1.554417
H 1.096951 4.144453 2.406716
H -0.444549 -1.755497 1.172315
H -2.812762 0.166578 -2.557188
H 0.759933 5.693114 1.612502
H 1.569315 -2.859493 -0.583418
H 3.433584 -2.323110 1.561758
H 3.931594 -0.641070 1.322311
H 2.577439 -1.038184 2.431022
pyruvic acid: intermediate E
43
scf done: -1426.558725
C -27.238404 -67.258391 18.219933
N -26.599449 -68.113557 19.138712
C -25.692350 -68.943044 18.595029
S -25.569733 -68.677638 16.906034
C -26.789024 -67.433434 16.944056
C -27.001576 -68.171404 20.583805
C -26.781704 -66.893487 21.355798
C -25.518488 -66.271107 21.558113
N -25.425784 -65.116064 22.250734
C -26.536524 -64.600851 22.782567
N -27.767205 -65.140162 22.699093
C -27.852791 -66.267190 21.985289
C -26.406414 -63.320930 23.562866
N -24.358743 -66.760423 21.043864
C -27.182801 -66.713498 15.681892
C -26.275495 -65.513175 15.349832
C -28.316137 -66.309401 18.649332
H -25.404893 -62.900580 23.451019
H -27.156367 -62.595468 23.229942
H -26.596525 -63.512619 24.626206
H -23.522277 -66.291936 21.370982
H -26.469115 -69.013343 21.019359
H -28.063920 -68.434336 20.596162
H -28.807279 -65.891964 17.767850
H -29.084173 -66.811834 19.246508
H -27.922750 -65.479230 19.243231
H -27.173188 -67.423748 14.846006
H -28.221033 -66.376092 15.774996
H -26.298709 -64.766875 16.151401
H -25.234668 -65.827151 15.212983
H -24.267986 -67.756536 20.830260
H -28.850096 -66.702755 21.906807
H -26.608648 -65.032106 14.423504
C -24.946309 -70.053710 19.272091
O -24.296835 -69.570572 20.442826
H -24.625416 -70.229388 21.121850
C -23.931327 -70.737886 18.351367
H -23.429690 -71.519278 18.929270
H -24.423675 -71.215679 17.498871
H -23.166396 -70.034366 18.000092
C -26.047361 -71.168910 19.751985
O -25.906393 -71.421826 20.974475
O -26.820421 -71.575828 18.880093
pyruvic acid: transition state 3 (TS3, F)
43
scf done: -1426.549728
C -2.361164 -0.778577 0.841565
C -1.991387 -0.527948 -0.508998
C -3.042028 -0.152278 -1.338370
N -4.306574 0.033972 -0.940328
C -4.533018 -0.162263 0.370594
N -3.624796 -0.564517 1.263226
C -0.595016 -0.705220 -1.065576
N 0.432499 0.228368 -0.530079
C 1.522467 -0.173816 0.212673
S 2.544883 1.210609 0.548415
C 1.516924 2.277377 -0.406885
C 0.451667 1.596793 -0.894360
C 1.933807 -1.443671 0.642458
O 0.951512 -2.445913 0.753913
C -0.634214 2.172778 -1.754297
C 1.889295 3.727861 -0.544655
C 1.597973 4.570007 0.712680
C -5.936329 0.071367 0.862501
N -1.480815 -1.212882 1.784599
C 3.041760 -1.561332 1.668204
C 3.037686 -2.189830 -1.188064
O 3.910770 -1.422297 -1.434873
O 2.409151 -3.201038 -1.355548
H -6.624185 -0.635083 0.382377
H -5.990497 -0.053572 1.945886
H -6.270745 1.078447 0.589124
H -1.900277 -1.480091 2.666523
H -0.222706 -1.708816 -0.878801
H -0.626354 -0.573632 -2.152500
H -0.380812 3.197945 -2.030965
H -0.766796 1.608208 -2.684273
H -1.599312 2.194114 -1.238263
H 2.956854 3.802338 -0.792302
H 1.353931 4.154973 -1.399732
H 0.529857 4.554069 0.956665
H 2.145501 4.190880 1.582947
H -0.641330 -1.717867 1.508663
H -2.853174 0.014446 -2.399683
H 1.898755 5.611967 0.552453
H 1.216352 -3.171554 0.148893
H 3.319519 -2.614305 1.781695
H 3.941451 -1.013608 1.367044
H 2.728944 -1.191617 2.657224
pyruvic acid: enamine (G)
40
scf done: -1237.965454
C -2.371176 -0.202582 0.940744
N -2.020687 0.050524 -0.423054
C -3.157591 -0.100381 -1.263519
S -4.473727 -0.968100 -0.411739
C -3.605181 -0.714643 1.133304
C -0.746182 -0.538294 -0.934098
C 0.522786 0.146154 -0.483048
C 0.816262 1.521363 -0.706288
N 1.993965 2.051053 -0.324489
C 2.888692 1.247685 0.263354
N 2.723253 -0.060945 0.506888
C 1.540533 -0.572206 0.125512
N -0.066662 2.373454 -1.288630
C 4.186056 1.878785 0.696231
C -3.279235 0.394551 -2.510565
C -4.458003 0.227299 -3.415110
C -4.319756 -1.055213 2.410974
C -5.433184 -0.063167 2.799297
C -1.392163 0.159632 2.021833
O -2.184679 1.087149 -3.043034
H 4.921977 1.107679 0.934744
H 4.572926 2.538189 -0.087385
H 4.024549 2.496362 1.589375
H 0.278491 3.294834 -1.520446
H -0.813969 -0.497414 -2.023807
H -0.692248 -1.602456 -0.656069
H -1.867939 0.108265 3.004130
H -0.521206 -0.504688 2.041229
H -1.017682 1.179323 1.877409
H -4.753515 -2.061361 2.314399
H -3.589167 -1.121581 3.224625
H -5.025149 0.942829 2.950536
H -6.198564 0.000654 2.018039
H -0.900619 2.032330 -1.753570
H 1.400564 -1.636127 0.322743
H -5.921754 -0.378550 3.729215
H -2.444622 1.495671 -3.882318
H -4.262061 -0.484795 -4.230605
H -5.331901 -0.131081 -2.863290
H -4.735408 1.189245 -3.873759
2-keto butanoic acid
13
scf done: -381.736975
C -2.159089 -1.074965 0.023464
C -1.419560 0.197898 0.497088
C -0.199553 0.460369 -0.339140
O -0.135749 1.277197 -1.244480
C 1.073481 -0.387641 -0.061097
O 2.078710 -0.104795 -0.898313
O 1.142155 -1.209549 0.821664
H -1.114279 0.068045 1.541169
H -2.072637 1.071929 0.415617
H -3.050139 -1.227620 0.640876
H -2.480291 -0.978566 -1.019304
H -1.523990 -1.960670 0.118982
H 1.761130 0.599220 -1.505652
2-keto-butanoic acidTS1 (B)
46
scf done: -1465.843547
C -27.480704 -66.731209 18.026590
N -27.554628 -67.695154 19.064499
C -27.071970 -68.919895 18.803443
S -26.461784 -68.917108 17.201203
C -26.888352 -67.239901 16.909885
C -28.197602 -67.415461 20.385044
C -27.477403 -66.417023 21.257251
C -26.241821 -66.677379 21.913217
N -25.636835 -65.717713 22.646145
C -26.252861 -64.542318 22.787133
N -27.458868 -64.224218 22.280670
C -28.032680 -65.171381 21.530374
N -25.587895 -67.865340 21.827293
C -25.555629 -63.483147 23.597853
C -27.017280 -70.781486 20.150564
C -28.358836 -71.251714 19.533442
O -29.394757 -71.015357 20.359558
C -26.576165 -66.564044 15.602271
C -25.125621 -66.053426 15.505855
C -28.040848 -65.349935 18.190311
O -27.074574 -70.361306 21.329641
C -25.771196 -71.422735 19.573295
C -24.457250 -70.815287 20.061529
O -28.477289 -71.799764 18.462015
H -25.426372 -62.573861 22.999528
H -26.168485 -63.210022 24.464953
H -24.581449 -63.838605 23.939508
H -24.793283 -67.952455 22.449360
H -28.274127 -68.387520 20.872662
H -29.216256 -67.065947 20.188030
H -28.056523 -64.839523 17.224340
H -29.070616 -65.370933 18.564664
H -27.448662 -64.741906 18.881638
H -26.771930 -67.263177 14.779543
H -27.268608 -65.726537 15.456380
H -24.913888 -65.318638 16.290568
H -24.408553 -66.874951 15.613051
H -26.082857 -68.734833 21.622700
H -29.008697 -64.917108 21.115031
H -24.952851 -65.577222 14.533869
H -25.831956 -72.477351 19.888716
H -25.836832 -71.443592 18.482366
H -23.607435 -71.363773 19.640392
H -24.369035 -69.765986 19.759902
H -24.383671 -70.862827 21.153016
H -28.990815 -70.654520 21.183301
2-keto-butanoic acid: initial complex (C)
46
scf done: -1465.865096
C -28.083475 -65.068100 21.512898
C -27.492659 -66.289462 21.211392
C -26.233891 -66.525569 21.841232
N -25.653183 -65.555806 22.586384
C -26.310938 -64.409651 22.764722
N -27.533073 -64.118378 22.277857
C -28.204465 -67.302546 20.353758
N -27.523736 -67.600165 19.038187
C -27.438512 -66.634151 18.014288
C -26.850357 -67.122226 16.884195
S -26.419457 -68.793045 17.114296
C -27.028715 -68.805364 18.715905
C -27.979747 -65.248115 18.192251
C -26.534465 -66.419658 15.590167
C -25.124270 -65.799749 15.557623
N -25.555845 -67.686746 21.709806
C -25.644779 -63.347376 23.597927
C -27.054069 -70.092915 19.564764
C -25.921023 -71.075031 19.121718
C -24.518832 -70.641576 19.555321
C -28.424578 -70.811980 19.182493
O -28.797201 -71.054905 18.052899
O -27.049533 -69.860524 20.906397
O -29.071768 -71.128372 20.295481
H -25.576068 -62.410792 23.032724
H -26.247637 -63.138120 24.489667
H -24.646442 -63.667083 23.903313
H -24.731174 -67.766001 22.292410
H -28.275238 -68.268833 20.854317
H -29.208491 -66.948556 20.102733
H -27.962204 -64.723882 17.234446
H -29.017428 -65.258497 18.542525
H -27.392538 -64.666585 18.908624
H -26.642724 -67.129112 14.760735
H -27.284664 -65.639946 15.416107
H -25.001714 -65.054616 16.351217
H -24.351461 -66.564666 15.692383
H -26.043163 -68.564609 21.435323
H -29.071540 -64.836591 21.111366
H -24.949482 -65.307036 14.594677
H -26.162871 -72.030078 19.602837
H -25.967800 -71.261197 18.040504
H -23.781451 -71.397624 19.260914
H -24.215643 -69.689304 19.103406
H -24.476538 -70.529361 20.642653
H -28.447888 -70.742139 21.003718
2-keto-butanoic acid: transition state 2 (TS2, D)
46
scf done: -1465.862559
C -26.993212 -68.801396 18.733446
N -27.506887 -67.599633 19.049454
C -27.436356 -66.640797 18.016754
C -26.845431 -67.128826 16.888954
S -26.388782 -68.791536 17.128441
C -28.197740 -67.295780 20.355850
C -27.489039 -66.286698 21.222980
C -28.076061 -65.059418 21.510595
N -27.528622 -64.108897 22.275989
C -26.314692 -64.403695 22.779834
N -25.663622 -65.556511 22.617169
C -26.241926 -66.524931 21.871446
N -25.564836 -67.691824 21.758171
C -25.652968 -63.342706 23.617522
C -27.993083 -65.259796 18.186073
C -26.545153 -66.434095 15.587023
C -25.138006 -65.808643 15.535133
C -27.030298 -70.090762 19.534275
O -27.063813 -69.898887 20.906190
C -25.915754 -71.084176 19.110785
C -24.505541 -70.674655 19.546207
C -28.452662 -70.789764 19.197244
O -29.036785 -71.000224 20.334938
O -28.814144 -71.050177 18.061971
H -25.621258 -62.393488 23.071260
H -26.238062 -63.167601 24.528608
H -24.641091 -63.645486 23.894295
H -24.753618 -67.773480 22.358930
H -28.299233 -68.255941 20.856903
H -29.194821 -66.931153 20.093780
H -27.969301 -64.737406 17.227546
H -29.035007 -65.278720 18.523561
H -27.419059 -64.670588 18.906878
H -26.659256 -67.150102 14.764011
H -27.300365 -65.658984 15.414842
H -25.010449 -65.056727 16.321571
H -24.360376 -66.569092 15.667551
H -26.052302 -68.563239 21.497297
H -29.057822 -64.824208 21.096508
H -24.975349 -65.322699 14.566660
H -26.176534 -72.034769 19.589957
H -25.963061 -71.271562 18.030238
H -23.780844 -71.443062 19.252541
H -24.185205 -69.727771 19.094845
H -24.459234 -70.564162 20.633958
H -28.183657 -70.515857 20.994977
2-keto-butanoic acid: intermediate E
46
scf done: -1465.870935
C -27.338632 -66.651073 18.093765
C -27.375908 -67.630875 19.126239
C -26.837851 -68.865690 18.781540
N -26.268597 -69.151361 17.604647
C -26.225102 -68.136146 16.723213
N -26.737095 -66.917493 16.916792
C -28.002639 -67.432274 20.484911
N -27.373244 -66.359321 21.326398
C -28.041966 -65.283163 21.785248
S -27.057023 -64.383376 22.864129
C -25.723596 -65.489545 22.684750
C -26.061063 -66.492389 21.825672
C -29.488170 -64.947090 21.597465
O -29.895277 -65.139918 20.250266
C -25.188501 -67.649027 21.442358
C -24.428790 -65.242418 23.412298
C -23.475207 -64.287810 22.668177
C -25.530079 -68.391767 15.413319
N -27.859571 -65.403364 18.239552
C -29.877729 -63.530335 22.067115
C -29.386872 -62.387127 21.168980
C -30.336454 -66.035351 22.511379
O -30.038879 -66.087105 23.705871
O -31.172815 -66.634935 21.792452
H -25.935193 -67.747233 14.629277
H -24.458820 -68.169832 15.511549
H -25.626304 -69.443228 15.130605
H -27.881507 -64.853449 17.389180
H -29.059902 -67.191497 20.421935
H -27.924824 -68.357664 21.063510
H -24.282074 -67.638617 22.050970
H -25.686479 -68.609726 21.611170
H -24.890753 -67.608228 20.390625
H -24.649764 -64.837924 24.407763
H -23.929127 -66.202071 23.584782
H -23.200905 -64.688987 21.686333
H -23.936218 -63.305894 22.513316
H -28.614633 -65.239355 18.908662
H -26.866129 -69.683658 19.503032
H -22.556746 -64.142920 23.247851
H -30.973782 -63.518371 22.088613
H -29.562807 -63.391045 23.108069
H -29.750715 -61.426645 21.552285
H -28.293129 -62.327142 21.117877
H -29.765472 -62.509222 20.149388
H -30.668112 -65.765662 20.376326
2-keto-butanoic acid: transition state 3 (TS3, F)
46
scf done: -1465.863382
C -26.064911 -66.605634 21.884901
N -27.350324 -66.450099 21.307747
C -28.036402 -65.336468 21.744590
S -27.017018 -64.415476 22.835593
C -25.722136 -65.605895 22.731781
C -27.946079 -67.513169 20.452731
C -27.349518 -67.653246 19.068434
C -27.450890 -66.673733 18.039071
N -26.868311 -66.869487 16.841530
C -26.232001 -68.025602 16.623062
N -26.139453 -69.041698 17.495609
C -26.700378 -68.822100 18.694348
N -28.103716 -65.490413 18.206315
C -25.568730 -68.193720 15.282246
C -29.361371 -64.922194 21.528918
C -30.416257 -66.045440 23.152401
O -31.218304 -66.624596 22.465837
C -24.461734 -65.388060 23.522760
C -23.549252 -64.283248 22.955625
C -25.219301 -67.799457 21.553228
O -30.030604 -65.437511 20.402328
C -29.793099 -63.507396 21.881967
C -29.384608 -62.448928 20.840836
O -29.939366 -65.743758 24.199726
H -26.259042 -67.922587 14.476541
H -24.703403 -67.523277 15.204521
H -25.230799 -69.223954 15.152350
H -28.218593 -64.946373 17.360132
H -29.010888 -67.303777 20.400814
H -27.832341 -68.463813 20.983980
H -24.312994 -67.789284 22.161415
H -25.738742 -68.742666 21.759188
H -24.916350 -67.809183 20.501742
H -24.727270 -65.141949 24.559972
H -23.903701 -66.329292 23.572591
H -23.227707 -64.524260 21.936215
H -24.064203 -63.316400 22.924359
H -28.842255 -65.408531 18.901467
H -26.620894 -69.643498 19.407588
H -22.655715 -64.169008 23.580314
H -30.887126 -63.507134 21.974343
H -29.410909 -63.234531 22.873132
H -29.753400 -61.458203 21.133281
H -28.295480 -62.385938 20.735612
H -29.808288 -62.689277 19.859517
H -30.810223 -65.928356 20.742099
2-keto-butanoic acid: enamine (G)
43
scf done: -1277.290087
C -25.912087 -66.659430 21.687772
C -27.246837 -66.397980 21.416898
C -27.755075 -65.213528 22.023668
N -26.978094 -64.456359 22.822178
C -25.708833 -64.832545 23.016165
N -25.120695 -65.907869 22.470986
C -28.029907 -67.293110 20.482558
N -29.279104 -67.889719 21.035647
C -29.163192 -68.991401 21.934204
C -30.011715 -70.014975 21.704215
S -31.059916 -69.703449 20.292525
C -30.364857 -68.059602 20.135916
C -28.176050 -68.911976 23.063704
C -30.901663 -67.124836 19.321581
C -32.052587 -67.330231 18.380123
C -33.363610 -66.671106 18.852425
C -30.213686 -71.295008 22.465917
C -31.489980 -71.326474 23.328955
N -29.035651 -64.791601 21.859673
C -24.878112 -63.969197 23.928992
O -30.424933 -65.808744 19.421611
H -24.960790 -62.915837 23.640047
H -25.243159 -64.049628 24.960706
H -23.832090 -64.281563 23.897919
H -29.257169 -63.878340 22.232779
H -28.332802 -66.727871 19.600050
H -27.366788 -68.098994 20.132770
H -28.317838 -69.747161 23.753382
H -27.137371 -68.943624 22.716474
H -28.300732 -67.980262 23.626615
H -30.243435 -72.130162 21.750926
H -29.339523 -71.477100 23.100640
H -31.469200 -70.534827 24.086674
H -32.387445 -71.180231 22.717750
H -29.625670 -65.165991 21.124935
H -25.439793 -67.538570 21.246544
H -31.582472 -72.291105 23.842628
H -31.783792 -66.929883 17.386562
H -32.214006 -68.402383 18.224289
H -34.156960 -66.812115 18.108596
H -33.697248 -67.110991 19.798553
H -33.234896 -65.594279 19.010203
H -30.469247 -65.375254 18.553902
2-keto-valeric acid
16
scf done: -421.052167
C -3.237330 -0.321911 0.339414
C -1.873691 -0.343319 -0.359159
C -0.852179 0.582554 0.351638
C 0.477775 0.555977 -0.342265
O 0.857819 1.382529 -1.157440
C 1.436553 -0.629646 -0.039805
O 1.182554 -1.500723 0.757996
O 2.568017 -0.576588 -0.752883
H -1.215012 1.615601 0.345447
H -0.726767 0.245292 1.386528
H -3.947549 -0.976097 -0.179129
H -3.156221 -0.670280 1.376100
H -3.662140 0.689286 0.354691
H -1.982774 -0.018929 -1.401899
H -1.482936 -1.367553 -0.375553
H 2.518787 0.228676 -1.313863
2-keto-valeric acid: TS1 (B)
49
scf done: -1505.158088
C -3.371516 -0.129548 -1.290294
C -2.145801 -0.531792 -0.770219
C -2.226975 -1.291413 0.430250
N -3.415390 -1.484412 1.042817
C -4.515104 -0.997145 0.465123
N -4.557980 -0.342883 -0.710600
C -0.857510 -0.225625 -1.493606
N 0.042728 0.755767 -0.813521
C -0.285185 2.128641 -0.670513
C 0.714738 2.822265 -0.057606
S 2.036462 1.724974 0.302303
C 1.242716 0.358554 -0.362936
C -1.575427 2.690039 -1.188032
C 2.202032 -1.730557 -0.410879
C 2.906657 -1.360808 -1.741254
O 3.908052 -0.689461 -1.835363
C 0.776741 4.277708 0.319430
C 0.420456 4.546538 1.794223
N -1.144117 -1.836490 1.043163
C -5.826503 -1.209771 1.172436
C 3.052902 -1.603089 0.836464
C 2.302365 -1.783105 2.157634
C 3.238793 -1.724801 3.370547
O 1.256259 -2.547743 -0.502563
O 2.290193 -1.918617 -2.799557
H -6.511776 -1.776290 0.531229
H -5.675504 -1.748549 2.109973
H -6.305359 -0.245023 1.377048
H -1.365392 -2.458137 1.811526
H -0.249263 -1.120903 -1.625240
H -1.080748 0.168215 -2.490413
H -1.550819 3.781153 -1.137997
H -1.747647 2.415437 -2.235131
H -2.438050 2.346649 -0.608286
H 1.784042 4.660477 0.112420
H 0.099686 4.846082 -0.329139
H -0.598797 4.214013 2.020090
H 1.103089 4.018430 2.469334
H -0.292369 -2.061131 0.526345
H -3.400491 0.403816 -2.241401
H 0.488451 5.618268 2.013645
H 3.812123 -2.397378 0.735647
H 3.613817 -0.664062 0.808642
H 1.530953 -1.007614 2.245516
H 1.776703 -2.745825 2.142718
H 2.681279 -1.854605 4.305692
H 4.000391 -2.513706 3.324759
H 3.762210 -0.761768 3.425764
H 1.574721 -2.477901 -2.415468
2-keto-valeric acid: initial complex (C)
49
scf done: -1505.179757
C -26.175974 -66.547008 21.928762
C -27.352714 -66.426474 21.199120
C -28.038071 -65.184390 21.356021
N -27.588296 -64.265861 22.243035
C -26.465139 -64.524757 22.913534
N -25.704987 -65.629315 22.781006
C -27.790265 -67.510441 20.249329
N -29.076315 -68.202830 20.637005
C -29.157283 -69.028355 21.777462
C -30.383096 -69.611309 21.914100
S -31.420096 -69.125547 20.603047
C -30.197735 -68.150880 19.901075
C -27.984303 -69.233552 22.687253
C -30.412437 -67.432943 18.553551
C -30.032413 -68.518132 17.446314
O -30.477677 -69.646034 17.388493
C -30.893187 -70.522217 22.999390
C -31.566635 -69.771695 24.164451
N -29.158294 -64.874163 20.667679
C -25.984118 -63.486828 23.892188
C -31.925304 -67.110766 18.330854
C -32.461597 -65.960564 19.190032
C -33.939111 -65.663525 18.903220
O -29.611440 -66.345287 18.378478
O -29.180200 -67.976800 16.588039
H -26.706549 -62.672434 23.976436
H -25.820424 -63.940860 24.876014
H -25.019587 -63.081385 23.563328
H -29.484112 -63.923085 20.790004
H -27.979595 -67.113312 19.251245
H -27.028981 -68.293543 20.191315
H -28.209323 -70.031816 23.397716
H -27.086797 -69.529780 22.133699
H -27.742000 -68.331526 23.256466
H -31.602429 -71.236771 22.564250
H -30.059885 -71.123490 23.380329
H -30.866801 -69.080451 24.646582
H -32.427669 -69.190078 23.816926
H -29.394478 -65.358787 19.777437
H -25.566486 -67.445685 21.819274
H -31.920169 -70.483169 24.919064
H -32.011869 -66.831830 17.273106
H -32.538353 -68.014619 18.454007
H -32.337763 -66.189096 20.257954
H -31.857127 -65.068846 18.990706
H -34.300096 -64.826274 19.512652
H -34.092647 -65.398656 17.849389
H -34.573227 -66.532685 19.121251
H -29.052355 -67.050357 16.997000
2-keto-valeric acid: transition state 2 (TS2, D)
49
scf done: -1505.177256
C -30.216372 -68.110137 19.918643
N -29.086011 -68.179169 20.643746
C -29.163977 -69.019461 21.774214
C -30.391295 -69.596777 21.913900
S -31.438627 -69.087853 20.619881
C -27.794469 -67.502330 20.256552
C -27.344466 -66.417130 21.201142
C -26.167457 -66.551169 21.929289
N -25.685119 -65.639133 22.780522
C -26.431322 -64.525816 22.915066
N -27.552472 -64.254648 22.245123
C -28.012641 -65.167839 21.360382
N -29.133977 -64.840505 20.676084
C -25.936698 -63.492868 23.891637
C -27.985720 -69.242044 22.673083
C -30.897682 -70.520310 22.990176
C -31.559027 -69.783520 24.170811
C -30.446467 -67.433683 18.578866
O -29.636242 -66.331155 18.358561
C -29.976912 -68.500924 17.452311
O -29.106937 -67.891073 16.710009
C -31.944196 -67.120256 18.324234
C -32.512111 -65.969379 19.164654
C -33.986949 -65.692496 18.846417
O -30.423667 -69.633317 17.379956
H -26.656301 -62.677333 23.987834
H -25.760802 -63.951125 24.871215
H -24.975975 -63.087402 23.551632
H -29.441320 -63.882850 20.794496
H -27.962226 -67.117117 19.253150
H -27.040313 -68.292522 20.206734
H -28.214828 -70.039562 23.382918
H -27.096451 -69.548497 22.111698
H -27.727944 -68.345306 23.243923
H -31.613253 -71.225469 22.550121
H -30.064530 -71.130960 23.356054
H -30.852497 -69.102120 24.657234
H -32.420279 -69.193471 23.838350
H -29.366680 -65.307575 19.785749
H -25.568533 -67.456570 21.818806
H -31.909758 -70.504120 24.918006
H -32.012379 -66.852206 17.262707
H -32.550184 -68.029338 18.440166
H -32.407503 -66.188767 20.236521
H -31.915744 -65.070242 18.971782
H -34.370688 -64.856313 19.443103
H -34.122914 -65.436482 17.788058
H -34.613632 -66.568641 19.057620
H -29.124876 -66.877756 17.318338
2-keto valeric acid: intermediate E
49
scf done: -1505.185652
C -26.030906 -66.581646 21.765438
N -27.307340 -66.397601 21.194361
C -27.904482 -65.233114 21.518310
S -26.893072 -64.310842 22.553077
C -25.646749 -65.528552 22.540491
C -27.982790 -67.493654 20.421162
C -27.325099 -67.850737 19.110225
C -27.185946 -66.968813 18.002283
N -26.558263 -67.372230 16.877474
C -26.123708 -68.632379 16.807598
N -26.266801 -69.563655 17.769091
C -26.858576 -69.143278 18.891784
N -27.629146 -65.683235 18.017171
C -25.435873 -69.062973 15.540490
C -29.310755 -64.804780 21.243153
C -29.588314 -63.314290 21.524392
C -28.978519 -62.326455 20.517827
C -29.347544 -60.873143 20.842666
C -24.366962 -65.311933 23.303086
C -23.329128 -64.466939 22.539566
C -25.243501 -67.836298 21.536167
O -29.709743 -65.131471 19.920072
C -30.267841 -65.700238 22.261322
O -31.125433 -66.327405 21.593355
O -30.010105 -65.612491 23.462319
H -25.275684 -68.209082 14.879176
H -24.477573 -69.540363 15.772388
H -26.047376 -69.810238 15.020005
H -27.582652 -65.211234 17.122129
H -29.016045 -67.184908 20.293748
H -27.992891 -68.368624 21.077917
H -24.359185 -67.834204 22.176413
H -25.823524 -68.732266 21.782611
H -24.909381 -67.929811 20.498827
H -24.598676 -64.830803 24.261482
H -23.934778 -66.286395 23.555370
H -23.049150 -64.944204 21.593996
H -23.719509 -63.469285 22.309513
H -28.397165 -65.414812 18.635580
H -26.967298 -69.892727 19.677271
H -22.423052 -64.344287 23.143357
H -30.680167 -63.207534 21.505455
H -29.289600 -63.072666 22.552378
H -27.884357 -62.424762 20.492464
H -29.335945 -62.582963 19.513656
H -28.921024 -60.181734 20.106226
H -30.435680 -60.732329 20.841328
H -28.977308 -60.577047 21.832667
H -30.529156 -65.680235 20.101012
2-keto valeric acid: transition state 3 (TS3, F)
49
scf done: -1505.178374
C -26.735492 -69.092686 18.806840
C -27.317598 -67.857939 19.062364
C -27.319583 -66.961504 17.955873
N -26.710373 -67.289947 16.800688
C -26.144063 -68.497168 16.699785
N -26.150141 -69.443749 17.652450
C -27.949223 -67.566844 20.407166
N -27.299971 -66.489458 21.203898
C -26.052258 -66.698492 21.843374
C -25.649560 -65.656374 22.608853
S -26.836914 -64.355873 22.551941
C -27.900547 -65.287338 21.513543
C -25.305903 -67.986282 21.657092
C -29.181141 -64.788632 21.219763
C -30.353289 -65.665364 22.907807
O -29.878384 -65.301623 23.936367
C -24.401509 -65.475033 23.427984
C -23.368503 -64.524110 22.793163
N -27.900312 -65.730905 18.001692
C -25.435734 -68.813752 15.409926
C -29.500748 -63.316835 21.425779
C -28.976754 -62.389249 20.310537
C -29.361629 -60.922705 20.538716
O -29.868764 -65.355000 20.129052
O -31.183798 -66.247308 22.257730
H -25.985609 -68.404033 14.557565
H -24.439200 -68.352327 15.408974
H -25.313471 -69.893514 15.298266
H -27.949681 -65.250973 17.111560
H -28.991552 -67.281125 20.296884
H -27.929400 -68.479478 21.011476
H -24.430820 -68.003070 22.309334
H -25.918395 -68.858715 21.912993
H -24.957813 -68.114347 20.627463
H -24.677208 -65.099661 24.422923
H -23.938905 -66.453678 23.595714
H -23.040305 -64.896763 21.816345
H -23.785771 -63.521584 22.645863
H -28.652079 -65.543537 18.661216
H -26.736928 -69.857311 19.584642
H -22.488160 -64.431024 23.439702
H -30.593832 -63.217426 21.477931
H -29.125085 -62.981733 22.401374
H -27.884415 -62.477735 20.241712
H -29.380218 -62.732309 19.349251
H -28.985363 -60.282710 19.731630
H -30.451548 -60.799604 20.580769
H -28.948972 -60.545258 21.483209
H -30.688120 -65.754088 20.495104
2-keto-valeric acid: enamine (G)
46
scf done: -1316.605251
C -26.394191 -69.015426 18.840024
N -26.675353 -67.677411 19.225964
C -26.765852 -66.813561 18.094699
C -26.689045 -67.425025 16.894378
S -26.508005 -69.194254 17.061074
C -27.644092 -67.486540 20.342412
C -27.381088 -66.313134 21.259405
C -28.362891 -65.359598 21.482975
N -28.243447 -64.306634 22.308687
C -27.065214 -64.205464 22.941917
N -26.044202 -65.063016 22.829862
C -26.184620 -66.120932 22.008068
N -25.120062 -66.961099 21.925658
C -26.862441 -63.025869 23.856360
C -26.878679 -65.331779 18.314685
C -26.685322 -66.841966 15.508994
C -25.300295 -66.821697 14.833328
C -26.000790 -70.026529 19.644620
O -25.748322 -69.733921 20.993662
C -25.698921 -71.431344 19.213047
C -24.193747 -71.777412 19.215934
C -23.923726 -73.233254 18.820391
H -26.464477 -63.353695 24.822649
H -26.128468 -62.334567 23.423051
H -27.804688 -62.493490 24.003166
H -24.374829 -66.803843 22.590768
H -27.623693 -68.412981 20.918348
H -28.660177 -67.388887 19.930237
H -26.767755 -64.796564 17.368847
H -27.843395 -65.042771 18.746422
H -26.099365 -64.978889 18.999431
H -27.381968 -67.417354 14.882003
H -27.088403 -65.823935 15.545788
H -24.594349 -66.211025 15.407808
H -24.881617 -67.831074 14.754941
H -25.207994 -67.883781 21.514521
H -29.317356 -65.442609 20.960679
H -25.372041 -66.403700 13.821859
H -26.229823 -72.140237 19.874416
H -26.111279 -71.608025 18.212734
H -23.677711 -71.098969 18.524594
H -23.776005 -71.579564 20.211994
H -22.849641 -73.452951 18.826792
H -24.410476 -73.932907 19.512648
H -24.301272 -73.447893 17.812485
H -25.945781 -70.510672 21.541489
2-keto-isovaleric acid
16
scf done: -421.050134
C -1.494560 -1.614516 -0.599088
C -1.303353 -0.091116 -0.432080
C -1.802433 0.402715 0.943538
C 0.132140 0.315444 -0.676953
O 0.479388 1.060736 -1.581077
C 1.270026 -0.217868 0.246533
O 1.092310 -0.961127 1.182317
O 2.474431 0.241827 -0.114163
H -1.142689 -1.959335 -1.578411
H -0.965650 -2.170015 0.180031
H -2.562753 -1.849158 -0.527910
H -1.870685 0.422777 -1.217271
H -1.668787 1.485039 1.055342
H -2.873782 0.189002 1.031267
H -1.280846 -0.102194 1.761078
H 2.339298 0.820636 -0.897243
2-keto-isovaleric acid: TS1 (B)
49
scf done: -1505.149024
C 3.300057 -0.127819 1.334259
C 2.123328 -0.546230 0.722486
C 2.305305 -1.259219 -0.495375
N 3.533749 -1.390199 -1.040595
C 4.578395 -0.889135 -0.377946
N 4.526596 -0.281345 0.821789
C 0.779350 -0.318942 1.370149
N -0.102443 0.676667 0.681776
C 0.194571 2.063772 0.685634
C -0.765881 2.787407 0.046725
S -2.013063 1.701379 -0.526244
C -1.246689 0.293379 0.087117
C 1.414705 2.612154 1.363127
C -2.113738 -1.784195 0.144140
C -2.896877 -1.424819 1.446005
O -3.911549 -0.770308 1.520752
C -0.833739 4.268161 -0.213351
C -0.297617 4.673474 -1.599858
N 1.277645 -1.818972 -1.185300
C 5.937431 -1.031238 -1.009042
C -2.920805 -1.935322 -1.156345
C -2.021264 -2.333665 -2.334025
O -1.128077 -2.547931 0.335869
C -3.899105 -0.823898 -1.564328
O -2.309493 -1.974606 2.524244
H 5.860796 -1.516918 -1.983937
H 6.404572 -0.046373 -1.124652
H 6.593788 -1.621261 -0.358573
H 1.560022 -2.408208 -1.959096
H 0.198849 -1.239200 1.407839
H 0.918509 0.027886 2.398627
H 1.349539 3.701706 1.412839
H 1.511124 2.244806 2.390917
H 2.335646 2.355802 0.830003
H -1.873517 4.603487 -0.112214
H -0.270730 4.796379 0.565210
H 0.754916 4.390928 -1.713474
H -0.864213 4.186263 -2.401216
H 0.411114 -2.085863 -0.713830
H 3.253769 0.364740 2.306278
H -0.378598 5.757789 -1.737869
H -3.536181 -2.816486 -0.898977
H -2.638125 -2.541573 -3.215841
H -1.333754 -1.518029 -2.588817
H -1.431987 -3.227323 -2.110463
H -4.609078 -1.229163 -2.295663
H -4.463730 -0.433291 -0.716667
H -3.375040 0.000131 -2.059351
H -1.562511 -2.508580 2.159658
2-keto-isovaleric acid: initial complex (C)
49
scf done: -1505.171662
C -26.034494 -66.345924 21.866431
C -27.273988 -66.275360 21.242395
C -28.021213 -65.089308 21.508626
N -27.553195 -64.173937 22.389294
C -26.359633 -64.379133 22.947759
N -25.547869 -65.427481 22.709054
C -27.719708 -67.356568 20.292070
N -28.979024 -68.073084 20.711809
C -29.023667 -68.846675 21.888017
C -30.233643 -69.448285 22.070144
S -31.292998 -69.053097 20.748862
C -30.107075 -68.084675 19.980166
C -27.832477 -68.991393 22.786618
C -30.300370 -67.392728 18.614699
C -29.566508 -68.332675 17.564903
O -29.656084 -69.543242 17.508686
C -30.714388 -70.312157 23.205918
C -31.394891 -69.515567 24.335795
N -29.220342 -64.835828 20.937886
C -25.859950 -63.345451 23.921609
C -31.805936 -67.235043 18.139118
C -32.567969 -66.224485 19.010559
O -29.684318 -66.171372 18.580771
C -32.647953 -68.498164 17.871782
O -28.837049 -67.581915 16.747757
H -26.596867 -62.550203 24.050797
H -25.647218 -63.810695 24.891223
H -24.918206 -62.915124 23.561188
H -29.590794 -63.911805 21.125288
H -27.941068 -66.943705 19.309258
H -26.945391 -68.123759 20.198008
H -28.016166 -69.790890 23.507773
H -26.930566 -69.256336 22.225243
H -27.620011 -68.074046 23.342934
H -31.411080 -71.064293 22.816064
H -29.864355 -70.873333 23.610321
H -30.706751 -68.784550 24.773902
H -32.271329 -68.972053 23.965756
H -29.483852 -65.289060 20.038411
H -25.385480 -67.202467 21.675614
H -31.726565 -70.193439 25.130230
H -31.648653 -66.749483 17.167293
H -33.526665 -65.978049 18.537846
H -32.792562 -66.620086 20.009473
H -31.993752 -65.301295 19.122924
H -33.491689 -68.226608 17.225179
H -32.078222 -69.284917 17.370322
H -33.084106 -68.921306 18.783933
H -28.945553 -66.662964 17.175077
2-keto-isovaleric acid: transition state 2 (TS2, D)
49
scf done: -1505.169389
C -30.128017 -68.052739 19.986824
N -28.995347 -68.048311 20.715280
C -29.039042 -68.831982 21.885501
C -30.247393 -69.436703 22.064260
S -31.311310 -69.030231 20.750702
C -27.727379 -67.349327 20.298017
C -27.269781 -66.264790 21.240629
C -26.029192 -66.349409 21.862499
N -25.529653 -65.435816 22.701917
C -26.326804 -64.376686 22.941012
N -27.518666 -64.158084 22.383366
C -27.998587 -65.069098 21.506579
N -29.198303 -64.797282 20.939732
C -25.812294 -63.347465 23.911324
C -27.847985 -68.982080 22.783388
C -30.724637 -70.314183 23.191094
C -31.401695 -69.531390 24.332613
C -30.336185 -67.397666 18.627808
O -29.719892 -66.151480 18.560116
C -29.519124 -68.288255 17.559924
O -28.771032 -67.466158 16.886576
C -31.824835 -67.254224 18.133311
C -32.638146 -68.534857 17.859564
O -29.625392 -69.500450 17.460704
C -32.618809 -66.250789 18.986232
H -26.543326 -62.548240 24.048849
H -25.592006 -63.815526 24.877761
H -24.872050 -62.921503 23.541805
H -29.550439 -63.865096 21.121586
H -27.918879 -66.956718 19.304075
H -26.961632 -68.126711 20.219785
H -28.037581 -69.776912 23.507992
H -26.948267 -69.256984 22.223196
H -27.628480 -68.064267 23.336168
H -31.422536 -71.061396 22.794043
H -29.873618 -70.880580 23.585895
H -30.712214 -68.805621 24.777345
H -32.279557 -68.983716 23.972194
H -29.463520 -65.237265 20.043252
H -25.391504 -67.214309 21.672071
H -31.730554 -70.218906 25.119857
H -31.661587 -66.774320 17.159930
H -33.577297 -66.030573 18.500541
H -32.846092 -66.640261 19.986786
H -32.068742 -65.312245 19.096411
H -33.470639 -68.283592 17.190859
H -32.038003 -69.312018 17.379594
H -33.088147 -68.957052 18.765435
H -29.045360 -66.517610 17.518094
2-keto-isovaleric acid: intermediate E
49
scf done: -1505.178797
C -25.969259 -66.387867 21.706836
N -27.284639 -66.250410 21.225811
C -27.918301 -65.128605 21.619745
S -26.871316 -64.169855 22.580623
C -25.577013 -65.325887 22.466238
C -27.952970 -67.352215 20.455422
C -27.295583 -67.703581 19.143225
C -27.127487 -66.806868 18.051103
N -26.522226 -67.213067 16.916390
C -26.128975 -68.486432 16.824395
N -26.294449 -69.426381 17.772483
C -26.868119 -69.005066 18.905453
N -27.518052 -65.504482 18.096290
C -25.431385 -68.904597 15.558328
C -29.366309 -64.802208 21.373627
C -29.907106 -63.420668 21.870127
C -29.933402 -63.185951 23.392261
C -24.254165 -65.061048 23.134890
C -23.265715 -64.274389 22.252644
C -25.145749 -67.608157 21.424257
O -29.619160 -64.882042 19.967599
C -30.246968 -65.991408 22.063470
O -31.161214 -66.364433 21.286592
O -29.898887 -66.358998 23.192595
C -29.296766 -62.222229 21.119377
H -25.693233 -68.236213 14.734734
H -24.343265 -68.860396 15.700851
H -25.687540 -69.937458 15.306878
H -27.461157 -65.016707 17.210332
H -28.988646 -67.056624 20.317192
H -27.963038 -68.224651 21.115718
H -24.254898 -67.598324 22.055962
H -25.695022 -68.528783 21.646167
H -24.820591 -67.656524 20.381024
H -24.427362 -64.514152 24.069724
H -23.806605 -66.017677 23.427160
H -23.041424 -64.818440 21.328707
H -23.672353 -63.295339 21.975758
H -28.268237 -65.215440 18.727931
H -26.996041 -69.762181 19.680618
H -22.325460 -64.111030 22.791016
H -30.955192 -63.486293 21.549719
H -29.885763 -61.321336 21.329546
H -28.266522 -62.008181 21.429095
H -29.304846 -62.387068 20.037998
H -30.600100 -62.341580 23.605344
H -30.298362 -64.061629 23.934129
H -28.950688 -62.921814 23.799789
H -30.454434 -65.433209 19.965346
2-keto-isovaleric acid: transition state 3 (TS3, F)
49
scf done: -1505.169448
C -3.379384 -0.067203 -1.360506
C -2.279290 -0.477561 -0.615417
C -2.590168 -0.958400 0.686404
N -3.854957 -0.916833 1.154947
C -4.817021 -0.461578 0.348463
N -4.643190 -0.049818 -0.919797
C -0.892961 -0.456773 -1.223426
N 0.101268 0.423363 -0.546719
C 0.009953 1.832336 -0.664169
C 1.083485 2.491686 -0.169144
S 2.259558 1.352336 0.472359
C 1.276198 -0.027486 0.024210
C -1.189421 2.473736 -1.296849
C 1.759639 -1.341684 0.180262
C 2.563914 -1.726232 -1.883488
O 3.220911 -0.804183 -2.254418
C 1.370044 3.965806 -0.085667
C 1.185953 4.561300 1.323711
N -1.651153 -1.451179 1.540100
C -6.219710 -0.417703 0.893012
C 2.920537 -1.737210 1.114049
C 2.484517 -1.689477 2.594977
O 0.769480 -2.350850 0.205631
C 4.286556 -1.046655 0.928199
O 2.086996 -2.821797 -2.039516
H -6.616425 0.602399 0.832904
H -6.877896 -1.052272 0.287956
H -6.240858 -0.757500 1.930472
H -2.024291 -1.882812 2.376591
H -0.461070 -1.452377 -1.240951
H -0.968965 -0.120735 -2.263289
H -1.033497 3.551650 -1.369336
H -1.370562 2.101644 -2.311626
H -2.099937 2.304568 -0.714242
H 2.398079 4.150161 -0.425989
H 0.722368 4.496486 -0.791985
H 0.154922 4.434121 1.672144
H 1.847270 4.077214 2.051195
H -0.786911 -1.842624 1.171415
H -3.233028 0.276798 -2.385379
H 1.417474 5.632798 1.318101
H 3.078799 -2.795632 0.865403
H 3.266679 -2.113234 3.237657
H 2.305395 -0.658336 2.923530
H 1.567312 -2.265565 2.754580
H 5.055687 -1.660667 1.412401
H 4.559043 -0.929797 -0.123844
H 4.330095 -0.061164 1.403134
H 1.022097 -2.999249 -0.486964
2-keto-isovaleric acid: enamine (G)
46
scf done: -1316.599624
C -3.477797 0.265624 -1.260639
N -2.316675 0.225273 -0.431252
C -2.636424 -0.268511 0.870837
C -3.888207 -0.749789 1.014780
S -4.818464 -0.658522 -0.509842
C -1.079614 -0.299464 -1.085903
C 0.231119 0.217731 -0.541789
C 1.210999 -0.659873 -0.097701
N 2.421183 -0.298483 0.353112
C 2.661369 1.023306 0.360425
N 1.813144 1.972090 -0.047108
C 0.602343 1.590005 -0.506196
N -0.226011 2.585285 -0.908116
C 4.008572 1.467993 0.866771
C -1.609235 -0.165111 1.963896
C -4.580114 -1.293764 2.233389
C -5.622629 -0.341661 2.850710
C -3.586877 0.990181 -2.394502
O -2.499194 1.820913 -2.701236
C -4.780748 1.118237 -3.325189
C -5.400152 -0.218114 -3.774173
C -5.844943 2.080307 -2.751523
H 4.166200 1.106456 1.889538
H 4.804798 1.035903 0.249072
H 4.086402 2.557180 0.848811
H 0.152977 3.521761 -0.926111
H -1.166955 -0.031629 -2.140917
H -1.074349 -1.399212 -1.031876
H -2.066945 -0.355382 2.937748
H -0.787256 -0.878486 1.839340
H -1.167818 0.837346 1.985292
H -5.072673 -2.240241 1.966273
H -3.828167 -1.550906 2.987540
H -5.153894 0.595456 3.172337
H -6.408986 -0.091892 2.129953
H -1.105727 2.395842 -1.375086
H 1.008286 -1.732143 -0.102496
H -6.097016 -0.805636 3.723984
H -4.389093 1.590283 -4.241655
H -6.655740 2.234322 -3.474601
H -6.280147 1.674331 -1.831984
H -5.405404 3.055974 -2.516018
H -6.140781 -0.036918 -4.562481
H -4.636829 -0.897459 -4.170067
H -5.914538 -0.732481 -2.956615
H -2.488889 2.009007 -3.652215
2-keto-3-methyl-valeric acid
19
scf done: -460.363494
C -2.941542 -0.858966 -0.561739
C -1.426144 -0.841863 -0.323737
C -0.864689 0.588990 -0.098746
C -1.331674 1.224713 1.229552
C 0.642932 0.592481 -0.201639
O 1.261868 1.189186 -1.070601
C 1.503552 -0.200732 0.828673
O 2.815835 -0.081880 0.592479
O 1.045200 -0.851570 1.737612
H -1.195904 1.224259 -0.930269
H -3.280275 -1.880425 -0.769408
H -3.498685 -0.500662 0.310839
H -3.218697 -0.234591 -1.420559
H -0.929276 -1.284321 -1.198247
H -1.171013 -1.468303 0.537583
H -0.883266 2.214583 1.374897
H -2.417671 1.359472 1.212615
H -1.070855 0.594643 2.084264
H 2.914058 0.491236 -0.200399
2-keto-3-methyl-valeric acid: TS1 (B)
52
scf done: -1544.461723
C -1.059541 0.569687 0.251012
N 0.166829 0.890091 0.701541
C 0.613526 2.218711 0.482267
C -0.313221 2.958179 -0.187476
S -1.717573 1.962369 -0.506103
C 0.989235 -0.100807 1.464787
C 2.244063 -0.569227 0.769910
C 3.505242 -0.229526 1.246706
N 4.661915 -0.597796 0.683115
C 4.549059 -1.349939 -0.427091
N 3.404414 -1.792134 -0.952797
C 2.246439 -1.442337 -0.353511
N 1.108515 -1.946382 -0.899389
C 5.828955 -1.747650 -1.112064
C 1.940606 2.701057 0.986724
C -0.242112 4.386950 -0.655014
C 0.168866 4.530947 -2.132957
C -2.136063 -1.370203 0.663547
O -1.222903 -2.212708 0.881086
C -2.745582 -0.756294 1.965100
O -2.128026 -1.244347 3.056159
C -3.076105 -1.588720 -0.537231
C -2.331583 -2.251454 -1.713176
C -3.253834 -2.772719 -2.823070
O -3.662547 0.029623 2.035960
C -3.966280 -0.422278 -0.993883
H 5.619206 -2.256781 -2.055001
H 6.450955 -0.864759 -1.295501
H 6.407288 -2.417423 -0.463778
H 1.259096 -2.657562 -1.604574
H 0.318897 -0.933960 1.668977
H 1.246956 0.360409 2.423151
H 2.004340 3.786095 0.875950
H 2.080258 2.473494 2.049568
H 2.778247 2.258630 0.438501
H -1.217601 4.864981 -0.500057
H 0.465958 4.936938 -0.024067
H 1.161181 4.101393 -2.310148
H -0.540778 4.019962 -2.793141
H 0.260778 -2.049165 -0.338469
H 3.592968 0.381269 2.146112
H 0.196807 5.588605 -2.419191
H -3.752846 -2.353721 -0.111978
H -1.621497 -1.525257 -2.133703
H -1.739205 -3.086326 -1.324870
H -2.672877 -3.313705 -3.579478
H -4.003868 -3.468133 -2.423422
H -3.787335 -1.965432 -3.336818
H -4.820812 -0.813774 -1.556173
H -4.352513 0.153418 -0.152115
H -3.422212 0.246879 -1.669058
H -1.484153 -1.907258 2.706530
2-keto-3-methyl-valeric acid: Initial complex (C)
52
scf done: -1544.484758
C -2.416520 -1.156651 0.695484
C -2.322419 -0.650368 -0.635320
C -3.537897 -0.404872 -1.262059
N -4.738262 -0.556958 -0.690737
C -4.716604 -0.972592 0.590513
N -3.624821 -1.277089 1.293487
C -1.022941 -0.463920 -1.374892
N -0.101067 0.565267 -0.769472
C 1.138311 0.281585 -0.332934
S 1.905221 1.709732 0.220843
C 0.524833 2.697375 -0.159822
C -0.463719 1.924195 -0.693022
C -1.786400 2.419892 -1.194393
C 0.534431 4.174110 0.133977
C 0.077476 4.518266 1.564781
C -6.049082 -1.125941 1.274296
N -1.332056 -1.502056 1.425132
C 1.807227 -1.107490 -0.373404
C 3.125579 -1.252913 0.502805
C 4.347953 -0.382131 0.143403
O 0.922453 -2.096759 -0.038394
C 2.220830 -1.328653 -1.891147
O 2.752969 -0.507417 -2.611970
O 1.893975 -2.563849 -2.253177
C 2.798272 -1.221920 2.010241
C 3.917871 -1.793372 2.891556
H -5.914734 -1.350885 2.334343
H -6.642590 -0.212425 1.158680
H -6.617749 -1.938204 0.804965
H -1.541057 -1.950373 2.309081
H -0.447895 -1.388274 -1.385689
H -1.211872 -0.142049 -2.403310
H -1.772461 3.511132 -1.237434
H -2.000737 2.053379 -2.203431
H -2.613778 2.115550 -0.547257
H 1.544470 4.567690 -0.033489
H -0.109498 4.684238 -0.591340
H -0.946968 4.175290 1.745791
H 0.726029 4.048171 2.312356
H -0.435615 -1.748664 0.957638
H -3.548043 -0.059449 -2.297388
H 0.109014 5.602235 1.721680
H 3.394100 -2.292360 0.269376
H 2.585379 -0.191818 2.331763
H 1.884503 -1.803400 2.167916
H 3.610527 -1.809680 3.944231
H 4.159354 -2.824026 2.600944
H 4.839655 -1.203360 2.827549
H 5.263328 -0.882624 0.478518
H 4.438503 -0.215875 -0.933162
H 4.331170 0.595210 0.640902
H 1.388493 -2.882683 -1.427636
2-keto-3-methyl-valeric acid: transition state 2 (TS2, D)
52
scf done: -1544.482503
C -0.449923 1.915222 -0.693130
N -0.099399 0.551951 -0.749436
C 1.141434 0.265918 -0.312278
S 1.921922 1.699057 0.212070
C 0.547744 2.689697 -0.180202
C -1.031903 -0.467601 -1.349586
C -2.332051 -0.646713 -0.606951
C -2.436115 -1.135997 0.727931
N -3.645985 -1.244820 1.322136
C -4.734209 -0.943913 0.611621
N -4.747374 -0.542684 -0.674064
C -3.544439 -0.402486 -1.241721
N -1.357207 -1.476655 1.472247
C -6.069903 -1.085537 1.290906
C 1.820958 -1.096514 -0.351070
C 2.122452 -1.421000 -1.900517
O 1.658150 -2.614005 -2.127350
C 0.571809 4.171882 0.084532
C 0.099404 4.549961 1.501643
C -1.771976 2.414777 -1.192343
C 3.164397 -1.239291 0.462680
C 2.917482 -1.178738 1.986024
C 4.083609 -1.733539 2.815992
O 0.946919 -2.109667 0.033869
C 4.367820 -0.381003 0.018463
O 2.676843 -0.647248 -2.665476
H -5.941273 -1.289576 2.355854
H -6.664236 -0.175729 1.153466
H -6.634266 -1.908271 0.834724
H -1.575298 -1.919068 2.356944
H -0.470113 -1.395337 -1.392300
H -1.226317 -0.138287 -2.374575
H -1.751827 3.505584 -1.241369
H -1.992822 2.044503 -2.198655
H -2.598340 2.119458 -0.539758
H 1.589106 4.549009 -0.076234
H -0.054734 4.675696 -0.660238
H -0.932110 4.224419 1.674605
H 0.730931 4.085941 2.267342
H -0.469114 -1.742258 1.015734
H -3.548558 -0.068315 -2.280642
H 0.143401 5.636265 1.637871
H 3.419073 -2.283386 0.235300
H 2.722285 -0.142933 2.299807
H 2.013824 -1.756059 2.207507
H 3.833773 -1.730628 3.883822
H 4.311035 -2.768968 2.531393
H 4.998984 -1.143638 2.690839
H 5.298598 -0.879278 0.311301
H 4.392560 -0.240723 -1.065155
H 4.382272 0.606552 0.495442
H 1.167350 -2.747821 -1.072636
2-keto-3-methyl-valeric acid: intermediate E
52
scf done: -1544.491865
C -3.525448 -0.564011 -1.237482
C -2.340139 -0.702263 -0.525011
C -2.500755 -1.027136 0.851715
N -3.729985 -1.105332 1.399103
C -4.792664 -0.919414 0.610365
N -4.751512 -0.670332 -0.710467
C -1.012311 -0.576574 -1.231878
N -0.099934 0.480782 -0.681079
C -0.456942 1.841882 -0.708998
C 0.541944 2.653354 -0.259436
S 1.925649 1.698054 0.185265
C 1.151009 0.231396 -0.247347
C -1.786164 2.301616 -1.227398
C 1.837466 -1.107344 -0.254611
C 1.881525 -1.608981 -1.809095
O 2.192502 -0.765286 -2.659343
C 0.560616 4.149944 -0.094555
C 0.090242 4.620101 1.295345
N -1.448915 -1.230975 1.690415
C -6.148980 -0.982060 1.259226
C 3.278875 -1.199839 0.352492
C 4.385867 -0.420268 -0.386154
O 1.014908 -2.048846 0.440924
C 3.302587 -0.967607 1.881718
C 4.569113 -1.510599 2.559051
O 1.555966 -2.819918 -1.885973
H -6.141872 -1.679912 2.100651
H -6.420886 0.007841 1.649934
H -6.907060 -1.273999 0.528380
H -1.702932 -1.582129 2.606027
H -0.458673 -1.510408 -1.213276
H -1.169107 -0.326391 -2.285705
H -1.771020 3.386547 -1.351642
H -2.014917 1.861455 -2.203178
H -2.605251 2.049880 -0.547768
H 1.575909 4.519394 -0.283210
H -0.069710 4.600397 -0.869702
H -0.939170 4.301763 1.492588
H 0.726030 4.211409 2.088618
H -0.549319 -1.541893 1.317334
H -3.487758 -0.350797 -2.306780
H 0.129061 5.713316 1.358529
H 3.492948 -2.266705 0.199290
H 3.216626 0.104604 2.108245
H 2.427202 -1.456334 2.323152
H 4.512575 -1.380044 3.646364
H 4.692907 -2.582650 2.358900
H 5.474315 -0.999110 2.212715
H 5.360303 -0.863823 -0.155058
H 4.247813 -0.451489 -1.469478
H 4.437403 0.631529 -0.079781
H 1.024563 -2.811082 -0.207732
2-keto-3-methyl-valeric acid: transition state 3 (TS3, F)
52
scf done: -1544.48266453
C -1.118942 0.190401 0.184237
N 0.137508 0.600774 0.585382
C 0.357900 1.996204 0.485153
C -0.699215 2.681043 -0.011020
S -2.021742 1.582440 -0.379068
C 1.104610 -0.266350 1.315659
C 2.432084 -0.501037 0.627101
C 3.617990 -0.105012 1.235747
N 4.840401 -0.266560 0.714980
C 4.878900 -0.854449 -0.493853
N 3.821423 -1.316072 -1.165987
C 2.597900 -1.174282 -0.614612
N 1.556311 -1.680349 -1.330028
C 6.233724 -1.016627 -1.129592
C 1.662243 2.601244 0.912685
C -0.865598 4.149956 -0.287893
C -0.734476 4.525231 -1.776711
C -1.720222 -1.082639 0.262088
O -0.819572 -2.172669 0.271296
C -2.303953 -1.129974 2.423573
O -1.922327 -2.246432 2.671665
C -3.007454 -1.479204 -0.488826
C -2.723567 -1.667460 -2.002222
C -3.850789 -2.371569 -2.769466
O -2.816569 -0.103168 2.746368
C -4.273903 -0.632990 -0.240131
H 6.877666 -1.632107 -0.490396
H 6.144795 -1.483974 -2.112421
H 6.722889 -0.040844 -1.229991
H 1.823423 -2.251330 -2.122372
H 0.593943 -1.205023 1.506398
H 1.289949 0.202464 2.288329
H 1.598202 3.689488 0.855257
H 1.918942 2.344209 1.946434
H 2.492149 2.279488 0.275973
H -1.846722 4.474881 0.083960
H -0.125753 4.709487 0.294938
H 0.253064 4.251698 -2.164827
H -1.487265 4.011883 -2.385530
H 0.690255 -1.930642 -0.857184
H 3.582125 0.381564 2.211580
H -0.870151 5.604663 -1.911524
H -3.222123 -2.479897 -0.086070
H -2.529027 -0.686281 -2.457649
H -1.802286 -2.252658 -2.108433
H -3.558139 -2.548531 -3.811498
H -4.085467 -3.346192 -2.321222
H -4.773211 -1.779934 -2.784115
H -5.162107 -1.235739 -0.458381
H -4.348849 -0.295184 0.796389
H -4.324462 0.247853 -0.889720
H -1.049115 -2.709687 1.060590
2-keto-3-methyl-valeric acid: enamine (G)
49
scf done: -1355.912878
C -1.152623 0.690207 0.058952
C 0.172612 0.752962 0.571105
C 0.772416 2.001519 0.476318
N 0.192375 3.097533 -0.034414
C -1.066436 2.931103 -0.473114
N -1.755038 1.786134 -0.449544
C 0.939243 -0.432900 1.108664
N 0.305365 -1.166304 2.244977
C 0.628193 -2.553521 2.340939
S 1.293005 -2.930742 3.962847
C 0.787948 -1.314437 4.536550
C 0.323363 -0.545172 3.530788
C 0.363233 -3.472212 1.387292
C 0.624802 -4.967616 1.405916
C 2.032629 -5.375241 1.880015
C -0.216555 0.850363 3.675639
C 0.897395 -1.022101 6.006970
C -0.157458 -1.734438 6.875702
C -1.754426 4.142948 -1.045195
N -1.889889 -0.448185 0.065321
O -0.371143 -3.017312 0.281532
C -0.511328 -5.705613 2.163702
C -0.479536 -7.233428 2.029865
H -1.181475 4.537231 -1.892613
H -2.765228 3.892341 -1.374106
H -1.802505 4.939917 -0.293847
H -2.782797 -0.418910 -0.407063
H 1.068673 -1.171904 0.315417
H 1.945881 -0.097774 1.403864
H -0.346337 1.101853 4.731054
H 0.442288 1.605935 3.233784
H -1.190289 0.940999 3.181680
H 1.900808 -1.312927 6.351001
H 0.830088 0.060029 6.164197
H -1.170452 -1.428716 6.589783
H -0.093552 -2.822599 6.765684
H -1.481211 -1.347411 0.294207
H 1.793474 2.131864 0.838732
H -0.011391 -1.490588 7.935015
H 0.559169 -5.290708 0.351724
H -0.464319 -5.423229 3.223431
H -1.471606 -5.330469 1.786331
H -1.356642 -7.680187 2.512976
H -0.489820 -7.543334 0.975891
H 0.409436 -7.671188 2.498014
H 2.225736 -6.424849 1.634497
H 2.802880 -4.767713 1.392271
H 2.153511 -5.266052 2.962483
H -0.187414 -3.580051 -0.486602
2-keto-4-methyl-pentanoic acid
19
scf done: -460.366625
C 2.819370 -0.438053 -0.953896
C 1.619429 -0.343923 0.000201
C 2.049666 0.156831 1.386496
C 0.529245 0.571819 -0.635468
C -0.752923 0.579799 0.141921
O -1.115830 1.472453 0.893226
C -1.696874 -0.648426 0.003417
O -1.468500 -1.583433 -0.727046
O -2.787252 -0.552487 0.773848
H 0.895869 1.602733 -0.691692
H 0.317184 0.206821 -1.647020
H 3.590778 -1.097235 -0.538520
H 2.524431 -0.839895 -1.930316
H 3.274188 0.548354 -1.114654
H 1.190234 -1.349007 0.102964
H 2.804728 -0.512239 1.815934
H 2.489281 1.160818 1.322953
H 1.212143 0.207265 2.091799
H -2.727733 0.303832 1.252425
2-keto-4-methyl-pentanoic acid: TS1 (B)
52
scf done: -1544.468644
C -1.071265 0.575697 0.411985
N 0.178751 0.914178 0.766158
C 0.593120 2.242940 0.491265
C -0.390263 2.959362 -0.122185
S -1.804999 1.941205 -0.318357
C 1.038165 -0.063643 1.504143
C 2.263463 -0.549350 0.770114
C 3.539410 -0.172786 1.176632
N 4.676960 -0.554285 0.585264
C 4.528895 -1.364030 -0.479958
N 3.370326 -1.845175 -0.934312
C 2.230965 -1.477025 -0.308680
N 1.084934 -2.024270 -0.788307
C 5.783881 -1.767976 -1.205838
C 1.948654 2.746277 0.886713
C -0.371084 4.380780 -0.616266
C -0.073180 4.505305 -2.122870
C -2.191456 -1.373485 0.766731
O -1.324156 -2.277138 0.846800
C -2.674731 -0.786318 2.119835
O -1.989952 -1.306848 3.156167
C -3.233517 -1.337557 -0.341219
C -2.859705 -2.009744 -1.674689
C -4.139213 -2.402414 -2.433500
O -3.577984 0.006215 2.255622
C -1.962366 -1.134073 -2.562402
H 5.556483 -2.480046 -2.001688
H 6.268630 -0.884211 -1.638253
H 6.498511 -2.212828 -0.504429
H 1.220441 -2.762018 -1.468597
H 0.372515 -0.889211 1.754023
H 1.335998 0.410489 2.444725
H 2.001448 3.826464 0.731803
H 2.159791 2.558344 1.945757
H 2.749311 2.284411 0.300559
H -1.337789 4.850789 -0.395937
H 0.375464 4.948509 -0.048395
H 0.908569 4.084270 -2.366753
H -0.823434 3.975611 -2.720473
H 0.236350 -2.091131 -0.223981
H 3.654908 0.480693 2.042264
H -0.079736 5.558435 -2.426574
H -4.082850 -1.884779 0.100754
H -3.606828 -0.318752 -0.487125
H -2.313177 -2.931629 -1.433888
H -3.895541 -2.896618 -3.381941
H -4.760875 -3.090396 -1.847121
H -4.747879 -1.518205 -2.667338
H -1.710332 -1.662756 -3.490540
H -2.476066 -0.203920 -2.840359
H -1.024223 -0.866448 -2.067973
H -1.398396 -1.987071 2.755986
2-keto-4-methyl-pentanoic acid: initial complex (C)
52
scf done: -1544.490663
C 1.185615 0.335689 -0.403457
N -0.041906 0.743215 -0.768284
C -0.314149 2.101309 -0.503107
C 0.740074 2.740920 0.080271
S 2.066993 1.634052 0.284429
C -1.023763 -0.125470 -1.522555
C -2.298290 -0.436856 -0.783475
C -3.523393 0.041396 -1.233118
N -4.703354 -0.206932 -0.653385
C -4.650556 -0.980993 0.448224
N -3.552163 -1.541458 0.955487
C -2.367679 -1.313477 0.340764
N -1.282613 -1.930484 0.855980
C -5.955166 -1.247355 1.150614
C -1.623940 2.730779 -0.869553
C 0.851383 4.166217 0.554168
C 0.436072 4.357996 2.025447
C 1.835599 -1.036574 -0.668249
O 0.942823 -2.059547 -0.768292
C 2.546178 -0.858019 -2.091303
O 2.190154 -1.863121 -2.878045
C 3.005819 -1.349955 0.330634
C 2.604102 -1.993200 1.672237
C 3.857956 -2.562442 2.359256
O 3.309666 0.038031 -2.387125
C 1.854570 -1.056849 2.633074
H -5.794927 -1.856963 2.042162
H -6.433551 -0.301928 1.431409
H -6.645706 -1.765650 0.474768
H -1.478528 -2.607423 1.583076
H -0.467601 -1.034355 -1.753126
H -1.244269 0.408782 -2.451289
H -1.562598 3.811140 -0.722604
H -1.879915 2.556627 -1.919967
H -2.448492 2.351823 -0.258890
H 1.883747 4.510026 0.416479
H 0.235953 4.804990 -0.089494
H -0.607167 4.063481 2.183511
H 1.060262 3.756434 2.695422
H -0.408236 -2.043408 0.303806
H -3.560326 0.667385 -2.126093
H 0.542731 5.409376 2.315082
H 3.641086 -2.071055 -0.198401
H 3.640493 -0.466698 0.491546
H 1.940828 -2.832441 1.427478
H 3.594337 -3.073798 3.293412
H 4.374646 -3.285254 1.716187
H 4.573027 -1.765951 2.608347
H 1.613569 -1.584531 3.564669
H 2.467062 -0.184531 2.899847
H 0.908728 -0.697735 2.214011
H 1.539497 -2.365139 -2.272322
2-keto-4-methyl-pentanoic acid: transition state 2 (TS2, D)
52
scf done: -1544.488253
C -2.381923 -1.323793 0.330394
C -2.308384 -0.424321 -0.773277
C -3.532038 0.076449 -1.203923
N -4.709600 -0.170578 -0.619712
C -4.658334 -0.967397 0.465148
N -3.561899 -1.552166 0.949997
C -1.035576 -0.104750 -1.514198
N -0.044637 0.742536 -0.752035
C 1.178987 0.321641 -0.379493
S 2.071386 1.612776 0.311989
C 0.756859 2.732811 0.099126
C -0.301217 2.104689 -0.487777
C 1.848475 -1.009722 -0.666307
C 3.019449 -1.354088 0.301825
C 2.640426 -2.026045 1.637470
C 1.881620 -1.119291 2.619085
C -1.603073 2.749089 -0.856754
C 0.884234 4.157591 0.570437
C 0.472939 4.357247 2.041754
C -5.959821 -1.233267 1.172733
N -1.300281 -1.967692 0.827147
O 0.968531 -2.068333 -0.817133
C 2.508502 -0.836524 -2.143883
O 3.290064 0.055855 -2.424876
O 2.050613 -1.811064 -2.864766
C 3.911312 -2.581748 2.303639
H -5.797124 -1.847795 2.060415
H -6.434619 -0.287960 1.459296
H -6.654592 -1.747408 0.497913
H -1.502102 -2.664968 1.533019
H -0.492760 -1.008155 -1.781905
H -1.261638 0.448656 -2.429973
H -1.532584 3.827329 -0.699420
H -1.854624 2.588253 -1.910430
H -2.434613 2.373279 -0.253599
H 1.920197 4.489547 0.430597
H 0.275574 4.801957 -0.073962
H -0.573257 4.074408 2.201740
H 1.091448 3.750705 2.712535
H -0.444493 -2.089961 0.264111
H -3.569031 0.720153 -2.083923
H 0.591306 5.408080 2.328786
H 3.646837 -2.061443 -0.253712
H 3.657571 -0.475901 0.473759
H 1.991733 -2.875751 1.388280
H 3.666226 -3.116833 3.229385
H 4.438352 -3.280174 1.642422
H 4.610635 -1.774631 2.562683
H 1.655417 -1.666804 3.542830
H 2.481347 -0.241712 2.896809
H 0.927452 -0.767772 2.212244
H 1.361801 -2.267312 -2.021292
2-keto-4-methyl-pentanoic acid: intermediate E
52
scf done: -1544.496534
C 3.570839 -0.160792 1.211017
C 2.343515 -0.537534 0.674491
C 2.421511 -1.240847 -0.559599
N 3.609153 -1.421179 -1.175122
C 4.712903 -0.974669 -0.571750
N 4.756226 -0.363743 0.626987
C 1.065604 -0.259366 1.428371
N 0.090369 0.641728 0.724655
C 0.375390 2.010646 0.535920
C -0.684543 2.702937 0.033296
S -2.039725 1.635188 -0.200390
C -1.160779 0.275377 0.371398
C 1.708868 2.594438 0.893175
C -1.853266 -1.023556 0.625589
C -2.237256 -0.994900 2.252199
O -2.925190 -0.047042 2.628647
C -0.790423 4.158584 -0.336991
C -0.442542 4.444833 -1.810436
N 1.329130 -1.733315 -1.202461
C 6.026155 -1.184679 -1.275569
C -3.175964 -1.241552 -0.149477
C -3.073578 -1.839104 -1.570491
C -2.348479 -0.953230 -2.595533
O -0.991456 -2.134983 0.444196
C -4.485223 -2.187833 -2.073045
O -1.740744 -1.998684 2.816645
H 5.870858 -1.650357 -2.250765
H 6.544598 -0.227364 -1.401949
H 6.678630 -1.822739 -0.667822
H 1.537695 -2.324084 -1.998326
H 0.523008 -1.168156 1.668679
H 1.299165 0.230875 2.378178
H 1.663468 3.682154 0.808962
H 1.996899 2.357743 1.922929
H 2.505716 2.237557 0.234040
H -1.808150 4.508626 -0.125258
H -0.132790 4.741482 0.317713
H 0.585405 4.142749 -2.038956
H -1.110534 3.902368 -2.488713
H 0.482195 -1.955734 -0.676168
H 3.601645 0.341411 2.179119
H -0.540392 5.515482 -2.022231
H -3.759077 -1.944216 0.458009
H -3.767484 -0.316825 -0.155141
H -2.508702 -2.775892 -1.480912
H -4.442136 -2.676829 -3.054001
H -5.001166 -2.866398 -1.382944
H -5.103764 -1.285888 -2.178610
H -2.304167 -1.459471 -3.568082
H -2.874788 -0.001121 -2.745970
H -1.317825 -0.727107 -2.300093
H -1.054128 -2.572556 1.344825
2-keto-4-methyl-pentanoic acid: transition state 3 (TS3, F)
scf done: -1544.490875
C -1.127222 0.253297 0.287682
N 0.113551 0.719321 0.666719
C 0.323293 2.097229 0.404523
C -0.724919 2.701259 -0.203985
S -2.026522 1.548893 -0.475647
C 1.097204 -0.067017 1.464358
C 2.391264 -0.410946 0.759138
C 3.602339 0.098864 1.208879
N 4.796340 -0.149875 0.651617
C 4.773296 -0.954909 -0.423200
N 3.685754 -1.550720 -0.923867
C 2.497556 -1.314562 -0.336221
N 1.423695 -1.964071 -0.865264
C 6.077452 -1.207236 -1.130972
C 1.607439 2.765988 0.796879
C -0.892495 4.120945 -0.671982
C -0.724865 4.300976 -2.193180
C -1.761205 -0.983124 0.528085
O -0.940532 -2.082792 0.842805
C -2.615480 -0.569530 2.504413
O -2.130494 -1.490325 3.117851
C -3.024700 -1.391493 -0.219570
C -2.810482 -2.199531 -1.525115
C -4.164212 -2.717576 -2.037336
O -3.328244 0.384390 2.445025
C -2.079350 -1.414504 -2.623929
H 6.138194 -2.246187 -1.468031
H 6.147411 -0.569236 -2.022058
H 6.918205 -0.972115 -0.474360
H 1.652839 -2.680186 -1.543429
H 0.579985 -0.964424 1.790093
H 1.325329 0.513951 2.363931
H 1.537947 3.837800 0.601800
H 1.827900 2.644103 1.863551
H 2.462100 2.378577 0.233741
H -1.884766 4.482525 -0.370332
H -0.171341 4.757980 -0.148422
H 0.276120 3.994644 -2.517011
H -1.454341 3.701121 -2.748911
H 0.592382 -2.123098 -0.299798
H 3.618116 0.755767 2.079242
H -0.869693 5.351403 -2.471391
H -3.618485 -2.022826 0.456085
H -3.651004 -0.513015 -0.421883
H -2.194535 -3.071420 -1.263889
H -4.033983 -3.341547 -2.930121
H -4.677859 -3.321622 -1.278948
H -4.828809 -1.885724 -2.308325
H -1.929177 -2.045493 -3.509187
H -2.660118 -0.537005 -2.937149
H -1.093910 -1.065939 -2.296663
H -1.194858 -2.361873 1.751129
2-keto-4-methyl-pentanoic acid: enamine (G)
49
scf done: -1355.919705
C -1.214425 0.848038 0.141343
C 0.137628 0.949036 0.578016
C 0.766809 2.138387 0.243018
N 0.192698 3.155077 -0.421887
C -1.089807 2.964124 -0.765176
N -1.807746 1.862434 -0.516637
C 0.897972 -0.151568 1.282262
N 0.305524 -0.644723 2.559518
C 0.516107 -2.017135 2.867445
S 1.201803 -2.196210 4.513135
C 0.880376 -0.465960 4.827307
C 0.440036 0.172066 3.723053
C 0.179028 -3.068735 2.090470
C 0.417975 -4.518012 2.395962
C -0.863134 -5.385723 2.510478
C -1.770674 -4.915429 3.655412
C 0.039148 1.618331 3.649391
C 1.078552 0.047351 6.226168
C -0.011049 -0.394268 7.222488
C -1.792952 4.081666 -1.490104
N -1.983515 -0.246433 0.376185
O -0.495421 -2.797798 0.891300
C -0.483426 -6.865325 2.670521
H -2.291473 3.701605 -2.388451
H -2.570729 4.516856 -0.849992
H -1.080722 4.863061 -1.763734
H -2.886271 -0.268406 -0.078374
H 0.967574 -1.023503 0.629264
H 1.926810 0.194335 1.466082
H 0.013547 2.058590 4.648975
H 0.728235 2.215803 3.042254
H -0.957034 1.722847 3.205124
H 2.058408 -0.292863 6.591774
H 1.131774 1.141476 6.203923
H -0.995545 -0.024129 6.914084
H -0.070492 -1.486307 7.287456
H -1.576997 -1.121767 0.686460
H 1.808626 2.290907 0.529405
H 0.203626 -0.004709 8.225028
H 1.064880 -4.953924 1.612871
H 0.991121 -4.603583 3.327026
H -1.428454 -5.284986 1.571177
H -1.377530 -7.498962 2.712532
H 0.137098 -7.216518 1.835968
H 0.082060 -7.027349 3.598054
H -2.692455 -5.509039 3.689850
H -1.265547 -5.023214 4.624160
H -2.049293 -3.862255 3.540672
H -0.321723 -3.504189 0.249189
Figures prepared with CYLview: Legault, C. Y. CYLview, version 1.0b,
Step 1 : ketoacids and Thiamine-diphosphate (ThDP) are infinitely separated. Energies are given in atomic unitssystem / QM Energy / thermal
correction / Gibbs
free energy
(298 KGgas phase) / water dielectric / dichloroethane dielectric
Total free energy (Gsolvent) / 298 KGsolvent / Total free energy (Gsolvent) / 298 KGsolvent
(ThDP) Ylide Form / -1084.112603 / 0.226234 / -1083.886368 / -1084.127427 / -1083.901193 / -1084.118903 / -1083.892669
pyruvic acid / -342.4168132 / 0.041257 / -342.375557 / -342.428363 / -342.387106 / -342.422129 / -342.380872
2-keto-butanoic acid / -381.7307293 / 0.068179 / -381.66255 / -381.741399 / -381.67322 / -381.73557 / -381.667391
2-Keto-isovaleric acid / -421.044297 / 0.094987 / -420.94931 / -421.053598 / -420.958611 / -421.048533 / -420.953546
2-keto-valeric acid / -421.0460136 / 0.094667 / -420.951347 / -421.055265 / -420.960598 / -421.049867 / -420.9552
2-keto-3-methyl-valeric acid / -460.3577722 / 0.121249 / -460.236523 / -460.365616 / -460.244367 / -460.360874 / -460.239625
2-keto-4-methyl-pentanoic acid / -460.3607678 / 0.121217 / -460.239551 / -460.367691 / -460.246474 / -460.36305 / -460.241833
Step 2: transition state of C-C bond formation (TS1) between ThDP and keto acids (B)
system / QM Energy / thermal
correction / Gibbs
free energy
(298 KGgas phase) / water dielectric / dichloroethane dielectric
Total free energy (Gsolvent) / 298 KGsolvent / Total free energy (Gsolvent) / 298 KGsolvent
pyruvic acid / -1426.529826 / 0.287432 / -1426.242394 / -1426.546427 / -1426.258995 / -1426.534827 / -1426.247395
2-keto-butanoic acid / -1465.843547 / 0.316616 / -1465.526931 / -1465.8593 / -1465.542684 / -1465.847814 / -1465.531198
2-Keto-isovaleric acid / -1505.149024 / 0.34311 / -1504.805915 / -1505.163643 / -1504.820533 / -1505.153052 / -1504.809942
2-keto-valeric acid / -1505.158088 / 0.342118 / -1504.81597 / -1505.171681 / -1504.829563 / -1505.160639 / -1504.818521
2-keto-3-methyl-valeric acid / -1544.461723 / 0.369909 / -1544.091815 / -1544.474166 / -1544.104257 / -1544.464045 / -1544.094136
2-keto-4-methyl-pentanoic acid / -1544.468644 / 0.369234 / -1544.09941 / -1544.480895 / -1544.111661 / -1544.470372 / -1544.101138
Step 3 : initial complex (C)
system / QM Energy / thermal
correction / Gibbs
free energy
(298 KGgas phase) / water dielectric / dichloroethane dielectric
Total free energy (Gsolvent) / 298 KGsolvent / Total free energy (Gsolvent) / 298 KGsolvent
pyruvic acid / -1426.551962 / 0.29205 / -1426.259912 / -1426.575363 / -1426.283313 / -1426.561939 / -1426.269889
2-keto-butanoic acid / -1465.865096 / 0.318915 / -1465.546181 / -1465.88568 / -1465.566765 / -1465.873086 / -1465.554171
2-Keto-isovaleric acid / -1505.171662 / 0.345782 / -1504.82588 / -1505.189949 / -1504.844167 / -1505.177924 / -1504.832142
2-keto-valeric acid / -1505.179757 / 0.345255 / -1504.834502 / -1505.199048 / -1504.853793 / -1505.186793 / -1504.841538
2-keto-3-methyl-valeric acid / -1544.484758 / 0.371461 / -1544.113297 / -1544.501792 / -1544.130331 / -1544.490352 / -1544.118891
2-keto-4-methyl-pentanoic acid / -1544.490663 / 0.372169 / -1544.118494 / -1544.507895 / -1544.135726 / -1544.496445 / -1544.124276
Step 4 : transition state for the internal proton transfer process : (TS2, D)
system / QM Energy / thermal
correction / Gibbs
free energy
(298 KGgas phase) / water dielectric / dichloroethane dielectric
total free energy (Gsolvent) / 298 KGsolvent / total free energy (Gsolvent) / 298 KGsolvent
pyruvic acid / -1426.549349 / 0.288374 / -1426.260975 / -1426.574734 / -1426.28636 / -1426.560916 / -1426.272542
2-keto-butanoic acid / -1465.862559 / 0.315925 / -1465.546634 / -1465.885032 / -1465.569107 / -1465.872332 / -1465.556407
2-Keto-isovaleric acid / -1505.169389 / 0.342886 / -1504.826504 / -1505.18959 / -1504.846704 / -1505.177418 / -1504.834532
2-keto-valeric acid / -1505.177256 / 0.342059 / -1504.835198 / -1505.198729 / -1504.85667 / -1505.186074 / -1504.844015
2-keto-3-methyl-valeric acid / -1544.482503 / 0.369423 / -1544.113081 / -1544.501475 / -1544.132052 / -1544.489809 / -1544.120386
2-keto-4-methyl-pentanoic acid / -1544.488253 / 0.368976 / -1544.119278 / -1544.507462 / -1544.138486 / -1544.49566 / -1544.126684
Step 5: intermediate E
system / QM Energy / thermal
correction / Gibbs
free energy
(298 KGgas phase) / water dielectric / dichloroethane dielectric
total free energy (Gsolvent) / 298 KGsolvent / total free energy (Gsolvent) / 298 KGsolvent
pyruvic acid / -1426.558725 / 0.292251 / -1426.266474 / -1426.590821 / -1426.29857 / -1426.574015 / -1426.281764
2-keto-butanoic acid / -1465.870935 / 0.319321 / -1465.551614 / -1465.899728 / -1465.580407 / -1465.884385 / -1465.565064
2-Keto-isovaleric acid / -1505.178797 / 0.348138 / -1504.830659 / -1505.205803 / -1504.857665 / -1505.190684 / -1504.842546
2-keto-valeric acid / -1505.185652 / 0.344623 / -1504.841028 / -1505.213229 / -1504.868606 / -1505.198068 / -1504.853445
2-keto-3-methyl-valeric acid / -1544.491865 / 0.374318 / -1544.117546 / -1544.517898 / -1544.14358 / -1544.503138 / -1544.12882
2-keto-4-methyl-pentanoic acid / -1544.496534 / 0.37201 / -1544.124525 / -1544.521595 / -1544.149585 / -1544.507401 / -1544.135391
Step 6 : transition State for the C-C bond breaking (TS3, F)
system / QM Energy / thermal
correction / Gibbs
free energy
(298 KGgas phase) / water dielectric / dichloroethane dielectric
total free energy (Gsolvent) / 298 KGsolvent / total free energy (Gsolvent) / 298 KGsolvent
pyruvic acid / -1426.549728 / 0.287792 / -1426.261935 / -1426.561705 / -1426.273913 / -1426.552093 / -1426.264301
2-keto-butanoic acid / -1465.863382 / 0.315682 / -1465.5477 / -1465.874074 / -1465.558392 / -1465.865019 / -1465.549337
2-Keto-isovaleric acid / -1505.169448 / 0.342155 / -1504.827293 / -1505.179195 / -1504.83704 / -1505.170707 / -1504.828552
2-keto-valeric acid / -1505.178374 / 0.341725 / -1504.83665 / -1505.186889 / -1504.845164 / -1505.178622 / -1504.836897
2-keto-3-methyl-valeric acid / -1544.482665 / 0.368343 / -1544.114321 / -1544.490803 / -1544.12246 / -1544.48249 / -1544.114147
2-keto-4-methyl-pentanoic acid / -1544.490875 / 0.369371 / -1544.121504 / -1544.498087 / -1544.128716 / -1544.490143 / -1544.120772
Step 7: energy of enamine and CO2(G)
system / QM Energy / thermal
correction / Gibbs
free energy
(298 KGgas phase) / water dielectric / dichloroethane dielectric
total free energy (Gsolvent) / 298 KGsolvent / total free energy (Gsolvent) / 298 KGsolvent
pyruvic acid / -1237.965454 / 0.278028 / -1237.687426 / -1237.982328 / -1237.7043 / -1237.97153 / -1237.693502
2-keto-butanoic acid / -1277.279364 / 0.304776 / -1276.974587 / -1277.295528 / -1276.990752 / -1277.284979 / -1276.980203
2-Keto-isovaleric acid / -1316.588723 / 0.332787 / -1316.255936 / -1316.604219 / -1316.271432 / -1316.593687 / -1316.2609
2-keto-valeric acid / -1316.594378 / 0.331341 / -1316.263037 / -1316.609265 / -1316.277924 / -1316.598946 / -1316.267605
2-keto-3-methyl-valeric acid / -1355.902204 / 0.357233 / -1355.544972 / -1355.915897 / -1355.558664 / -1355.905745 / -1355.548512
2-keto-4-methyl-pentanoic acid / -1355.909129 / 0.357839 / -1355.551291 / -1355.920859 / -1355.56302 / -1355.911175 / -1355.553336
CO2 / -188.5903925 / -0.006203 / -188.596596 / -188.591178 / -188.597381 / -188.590416 / -188.596619
optimization at gas phase and single point in dichloroethane / optimized in dichloroethane dielectrics
System / Egs / Total free energy in solvent (single point calculation) / total G in solution at 298 K / total G in solution / total G in solution at 298 K
2-keto-butanoic acid / -381.7307293 / -381.73557 / -381.667391 / -381.735656 / -381.668106
Ylide / -1084.112603 / -1084.118903 / -1083.892669 / -1084.119039 / -1083.89337
TS1 / -1465.843547 / -1465.847814 / -1465.531198 / -1465.847938 / -1465.532511
barrier height (kcal/mol) / 18.11 / 18.18
Justification for the single point solvation calculation, compared to the optimization of molecule in solvent dielectrics. Egs is the energy of the optimized molecule at gas phase. Gsolv is the solvation energy of the molecule at dichloroethane dielectric.
Docking Analysis
Ligand / Score / GScore / Lipo / HBond / Metal / Rewards / vdW / Coul / RotB / Site / Emodel / CvdW / Internpyruvic acid / -10.7 / -10.7 / -- / -2.3 / -- / -- / -12.3 / -21.9 / -- / -- / -43.1 / -34.2 / 0
2-keto-butanoic acid / -11.63 / -11.63 / -- / -2.7 / -- / -- / -9.8 / -21.7 / -- / -- / -33.8 / -31.6 / 0.8
2-keto-isovaleric acid / -11.56 / -11.56 / -- / -2.5 / -- / -- / -14.3 / -22 / -- / -- / -46.9 / -36.3 / 0.9
2-keto-valeric acid / -11.31 / -11.31 / -- / -2.4 / -- / -- / -13.5 / -21.7 / -- / -- / -39.7 / -35.2 / 1.2
2-keto-3-methyl-valeric acid / -11.27 / -11.27 / -- / -2.7 / -- / -- / -8.1 / -21.7 / -- / -- / -27.7 / -29.8 / 2.4
2-keto-4-methyl-pentanoic acid / -11.01 / -11.01 / -- / -0.3 / -- / -- / -5.6 / -20.3 / -- / -- / -19.5 / -25.9 / 2.4
Phenyl pyruvic acid / X / X
Docking of different ketoacids on the active site of the pyruvate ferredoxin oxidoreductases (PDB: 2PDA) using Glide extra-precision method. GScore = a * vdW + b * Coul + Lipo + Hbond + Metal + Rewards + RotB + Site, where,
vdW = van der Waals interaction energy
Coul = Coulomb interaction energy
Lipo = Lipophilic-contact plus phobic-attractive term
HBond = Hydrogen-bonding term
Metal = Metal-binding term (usually a reward)
Rewards = Various reward or penalty terms
RotB = Penalty for freezing rotatable bonds
Site = Polar interactions in the active site,
and the coefficients of vdW and Coul are: a = 0.050, b = 0.150 for Glide 5.0(the contribution from the Coulomb term is capped at -4 kcal/mol)