Jing Zhang Le Li Yu Li Guangbin Zhang* Aqun Zheng Junjie Zhang Yang Sun*

Supplementary Material

Immobilization of chiral (salen)Manganese(III) complexes into mesoporous helical silica for asymmetric epoxidation of alkenes

Jing Zhang · Le Li · Yu Li · Guangbin Zhang* · Aqun Zheng · Junjie Zhang · Yang Sun*

Jing Zhang · Le Li · Yu Li · Aqun Zheng · Junjie Zhang · Yang Sun*

Department of Applied Chemistry, School of Science, Xi’an Jiaotong University, Xi’an, No. 28, Xianning West Road 710049, PR China

Tel.: + 86 29 82663914; fax: +86 29 82668559.

E-mail addresses: (Y. Sun)

Guangbin Zhang*

School of Pharmacy, Health Science Center, Xi’an Jiaotong University, Xi’an, No. 76, Yanta West Road 710061, PR China

E-mail address: (G. Zhang)

Table of Contents

1. Synthesis of helical silica (Page 1)

2. Synthesis of Mn2, Mn1, and Mn3 (Page 2)

3. Synthesis of H1 and H3 (Page 7)

4. Synthesis of Mn5, Mn4, and Mn6 (Page 7)

5. Synthesis of H4 and H6 (Page 11)

6. Pore distribution of C1, H2 and H5 (Page 12)

7. Powdered X-ray diffraction of synthetic samples (Page 12)

8. XPS measurement of C 1s region for helical silica, C1, H2, C2 and H5 (Page 13)

9. Adsorption kinetic profiles of L-valine and D-valine on helical silica, C1, C2, and six heterogeneous catalysts (Page 13)

10. Degradation of helical morphology (Page 15)

11. HPLC separation details and representative chromatograms (Page 16)

1. Synthesis of helical silica

Based on the mechanism of entropy-driven helix formation (Snir Y, Kamien RD (2005) Science 307: 1067-1067), helical silica was synthesized according to a sol-gel transcription procedure developed by Ying and co-workers, where cetyltrimethylammonium bromide (C16TAB) and commercial ammonia (25 wt%) were selected as surfactant and co-surfactant respectively (Han Y, Zhao L, Ying JY (2007) Adv Mater 19: 2454-2459). FT-IR (KBr) σ, cm-1: 3438 (br, s, SiO-H), 1107 (s, Si-O) and 802 (w, Si-O), as well as 622 (Si-C). Found in elemental analysis: C, 10.50; H, 2.22; N, 0.63.

2. Synthesis of Mn2, Mn1, and Mn3

Both homogeneous chloromethylated (salen)Mn(III) (Mn1, Mn2, Mn3) and their free ligands were synthesized according to the established procedure with minor modification (Yu K, Gu Z, Ji R, Lou L, Ding F, Zhang C, Liu S (2007) J Catal 252: 312-320). Mn2 and its free ligand were prepared as follows, while synthesis of Mn1 and Mn3 was almost identical to Mn2 except for the employment of corresponding diamine, as shown in Supplementary data.

Mn2

Free ligand of Mn2 was prepared firstly. The (R,R)-1,2-diammoniumcyclohexane mono-(+)-tartrate salt (2.56 g, 9.71 mmol) were combined with anhydrous K2CO3 (2.68 g, 19.42 mmol) in distilled water (15 mL) into a round-bottomed flask (100 mL) under stirring at room temperature. Then, absolute ethanol (6 mL) was introduced, the cloudy solution was heated at 75 oC for 2 h with vigorous stirring, and cooled to room temperature. Free diamine was carefully extracted by CH2Cl2 (4×5 mL), then slowly added to a pre-prepared ethanol solution of 3-tert-butyl-5-chloromethyl-2-hydroxybenzaldehyde (4.39 g, 19.42 mmol, in 20 mL). The orange solution was refluxed at 80 oC for 3 h under vigorous stirring. After removal of solvent under reduced pressure, crude product was dissolved in CH2Cl2 (30 mL), and organic layer was washed with distilled water (3×20 mL), brine (3×20 mL), dried over anhydrous Na2SO4, and filtered. Solvent was utterly removed by rotary evaporation, and free ligand of Mn2 was obtained as yellow sticky solid (3.71 g, 72%). 1H NMR (400 MHz, CDCl3) δH, ppm: 1.40 (18H, s, C(CH3)3), 1.44-1.95 (8H, m, CH2 on cyclohexyl), 3.30-3.32 (2H, m, CH on cyclohexyl), 4.36 (4H, s, CH2 on methylene), 7.01 (2H, d, J = 8.0 Hz, ArH), 7.23 (2H, d, J = 7.6 Hz, ArH), 8.30 (2H, s, CHN), 13.79 (2H, br, s, ArOH). 13C NMR (100 MHz, CDCl3) δC, ppm: 24.9, 29.1, 34.5, 35.7, 66.1, 73.0, 73.3, 117.8, 126.9, 130.3, 137.1, 159.8, 166.1. FT-IR (KBr) σ, cm-1: 3423 (br, s, ArO-H), 2958 and 2868 (s, C-H on methyl), 2912 (s, C-H on methylene), 1619 (s, C=N), 1540 (w, C-O), 1437 (s, phenyl), 1389 (s, C-H on -CH2Cl), 1267 (m, Ar-OH), 670 (w, C-Cl on -CH2Cl). Ideal formula of free ligand of Mn2 was C30H40O2N2Cl2. Anal. Calcd.: C, 67.8; H, 7.5; N, 5.2. Found: C, 67.6; H, 7.9; N, 5.9. ESI-HRMS (positive, m/z): 554.5491 (Calcd. for [M+Na]+ 554.5453). = +302 (c 0.01 g mL-1, CH2Cl2).

Mn2 was prepared secondly. Free ligand (2.65 g, 5.0 mmol) and Mn(OAc)2·4H2O (1.34 g, 5.5 mmol) were combined with absolute ethanol (15 mL) into a round-bottomed flask (100 mL), and the brown solution was reflux at 80 oC for 3 h with vigorous stirring under nitrogen protection. Then LiCl·H2O (0.91g, 15 mmol) was added and nitrogen protection was removed, the mixture was further refluxed at 80 oC for an additional hour in air. After being cooled to room temperature, total solvent was removed by rotary evaporation, and residue was diluted in CH2Cl2 (100 mL). The organic layer was carefully washed with distilled water (3×50 mL) and brine (3×50 mL), dried over anhydrous Na2SO4, and filtered. After removal of solvent under reduced pressure, the product was obtained as brown powders (2.61 g, 81% yield based on the mole of free ligand). FT-IR (KBr) σ, cm-1: 3443 (br, s, HO-H), 2965 and 2869 (both m, C-H on methyl), 2932 (m, C-H on methylene), 1612 (s, C=N), 1539 (w, C-O), 1439 (s, phenyl), 1267 (m, Ar-OH), 670 (w, C-Cl on -CH2Cl), and 420 (w, Mn-N). Ideal formula of Mn2 was C30H38O2N2Cl3Mn·H2O. Anal. Calcd.: C, 56.49; H, 6.27; N, 4.39. Found: C, 56.66; H, 6.97; N, 4.40. Mn3+ was 1.72 mmol g-1 determined by ICP-AES (1.56 mmol g-1 as ideal value based on formula). = +97 (c 0.01 g mL-1, CH2Cl2).

Mn1

Free ligand of Mn1 was prepared as follows: ethylenediamine (0.4 mL, 0.36 g, 6 mmol) and 3-tert-Butyl-5-chloromethyl-2-hydroxybenzaldehyde (1.70 g, 12.3 mmol) were combined with absolute ethanol (20 mL) into a round-bottomed flask (100 mL), and the orange solution was reflux at 80 oC for 6 h under vigorous stirring. After being cooled at room temperature, total solvent was removed under reduced pressure, and residue was diluted with CH2Cl2 (100 mL). The organic layer was carefully washed with distilled water (3×50 mL) and brine (3×50 mL), dried over anhydrous Na2SO4, then filtered. After complete removal of solvent under rotary evaporation, the product was obtained as yellow sticky solid (2.76 g, 96% yield). 1H NMR (400 MHz, CDCl3) δH, ppm: 1.39 (18H, s, C(CH3)3), 1.90-1.99 (4H, m, CH2 on ethylenediamine backbone), 4.33 (4H, s, CH2 on methylene), 6.99 (2H, d, J = 8.0 Hz, ArH), 7.26 (2H, d, J = 8.0 Hz, ArH), 8.51 (2H, s, CHN), 13.66 (2H, br, s, ArOH). 13C NMR (100 MHz, CDCl3) δC, ppm: 33.7, 35.9, 68.6, 73.1, 74.0, 117.4, 124.4, 130.3, 138.3, 156.8, 160.9. FT-IR (KBr) σ, cm-1: 3390 (br, s, ArO-H), 2963 and 2871 (C-H on methyl), 2930 (C-H on methylene), 1639 (C=N), 1538 (C-O), 1436 (phenyl), 1266 (Ar-OH). Ideal formula of free ligand of Mn1 was C26H34O2N2Cl2. Anal. Calcd.: C, 65.4; H, 7.1; N, 5.8. Found: C, 65.3; H, 6.3; N, 6.0. ESI-HRMS (positive, m/z): 478.4569 (Calcd. for [M+H]+ 478.4427).

Mn1 was prepared as follows: free ligand (2.38 g, 5 mmol) and Mn(OAc)2·4H2O (1.34 g, 5.5 mmol) were combined with absolute ethanol (15 mL) into a round-bottomed flask (100 mL), and the brown mixture was reflux at 80 oC for 3 h under vigorous stirring. Then LiCl·H2O (0.91g, 15 mmol) was introduced, and the mixture was further refluxed at 80 oC for an additional hour under vigorous stirring in air. After being cooled to room temperature, total solvent was removed by rotary evaporation, and the residue was diluted in CH2Cl2 (100 mL). The organic layer was carefully washed with distilled water (3×50 mL) and brine (3×50 mL), dried over anhydrous Na2SO4, and filtered. After complete removal of solvent under reduced pressure, the product was obtained as brown powders (2.11 g, 69% yield based on the mole of free ligand). FT-IR (KBr) σ, cm-1: 3405 (br, s, HO-H), 2963 and 2869 (both m, C-H on methyl), 2933 (m, C-H on methylene), 1625 (s, C=N), 1559 (w, C-O), 1269 (w, Ar-OMn), 570 (w, Mn-O). Ideal formula of Mn1 was C26H32O2N2Cl3Mn·2.5H2O. Anal. Calcd.: C, 51.1; H, 6.0; N, 4.5. Found: C, 51.0; H, 5.1; N, 5.3. Mn3+ was 1.87 mmol g-1 determined by ICP-AES (1.63 mmol g-1 as ideal value based on formula).

Mn3

Synthesis of Mn3 was strictly identical to Mn2 except for substitution of (R,R)- 1,2-Diammoniumcyclohexane mono-(+)-tartrate salt with molarly equivalent (S,S)-1,2-Diammoniumcyclohexane mono-(-)-tartrate salt during ligand preparation. For free ligand of Mn3, 1H NMR (400 MHz, CDCl3) δH, ppm: 1.40 (18H, s, C(CH3)3), 1.46-1.90 (8H, m, CH2 on cyclohexyl), 3.30-3.34 (2H, m, CH on cyclohexyl), 4.30 (4H, s, CH2 on methylene), 6.97 (2H, d, J = 6.0 Hz, ArH), 7.25 (2H, d, J = 6.0 Hz, ArH), 8.31 (2H, s, CHN), 13.36 (2H, br, s, ArOH). 13C NMR (100 MHz, CDCl3) δC, ppm: 24.6, 29.9, 33.9, 34.6, 63.1, 73.0, 73.2, 117.9, 126.4, 130.3, 138.1, 159.8, 166.9. FT-IR (KBr) σ, cm-1: 3423 (br, s, ArO-H), 2958 and 2869 (m, C-H on methyl), 2912 (m, C-H on methylene), 1625 (s, C=N), 1541 (w, C-O), 1436 (s, phenyl), 1267 (m, Ar-OH). Ideal formula of free ligand of Mn3 was C30H40O2N2Cl2. Anal. Calcd.: C, 67.8; H, 7.5; N, 5.2. Found: C, 67.3; H, 6.9; N, 6.1. ESI-HRMS (positive, m/z): 554.5201 (Calcd. for [M+Na]+ 554.5453). = -68 (c 0.01 g mL-1, CH2Cl2).

For Mn3, obtained as brown powders, yield 55% based on the mole of free ligand, FT-IR (KBr) σ, cm-1: 3440 (br, s, HO-H), 2966 and 2867 (both m, C-H on methyl), 2929 (m, C-H on methylene), 1627 (s, C=N), 1559 (w, C-O), 1268 (w, Ar-OMn), 420 (w, Mn-N). Ideal formula of Mn3 was C30H38O2N2Cl3Mn·3H2O. Anal. Calcd.: C, 53.4; H, 5.6; N, 4.1. Found: C, 53.3; H, 5.9; N, 5.1. Mn3+ was 1.66 mmol g-1 determined by ICP-AES (1.48 mmol g-1 as ideal value based on formula). = -203 (c 0.01 g mL-1, CH2Cl2).

3. Synthesis of H1 and H3

H1

Mn1 (300 mg, 0.5 mmol) and C1 (1.0 g) were combined with CH2Cl2 (30 mL) into a round-bottomed flask (100 mL), and this suspension was heated at 40 oC for 48 h under vigorous stirring. After being cooled to room temperature, the brown solids were collected by filtration under reduced pressure, thoroughly washed with absolute ethanol (6×20 mL), and dried in air. H1 was obtained as brown powders (1.15 g). FT-IR (KBr) σ, cm-1: 3445 (br, s, SiO-H or HO-H), 2959 and 2867 (m, C-H on methyl), 2930 (m, C-H on methylene), 1633 (s, C=N), 1545 (w, C-O), 1433 (s, phenyl), 1090 (s, Si-O) and 799 (w, Si-O), and 620 (w, Si-C) cm-1. Mn3+ was 0.33 mmol g-1 determined by ICP-AES. = +209 (c 0.01 g mL-1, CH2Cl2).

H3

Synthesis of H3 was strictly identical to H2 except for substitution of Mn2 with molarly equivalent Mn3. H3 was obtained as brown powders (1.11 g). FT-IR (KBr) σ, cm-1: 3440 (SiO-H or HO-H), 2961 and 2869 (C-H on methyl), 2933 (C-H on methylene), 1619 (C=N), 1545 (C-O), 1430 (phenyl), 1091 and 801 (both for Si-O), and 622 (Si-C) cm-1. Mn3+ was 0.19 mmol g-1 determined by ICP-AES.

4. Synthesis of Mn5, Mn4, and Mn6

Both sulfonato-(salen)Mn(III) (Mn5, Mn4, Mn6) and their free ligands were synthesized according to literature (Zhang Z, Guan F, Huang X, Wang Y, Sun Y (2012) J Mol Catal A 363-364: 343-353).

Mn5

Mn5 and its free ligand were characterized as follows, synthesis of Mn4 and Mn6 was almost identical to Mn5 except for the employment of corresponding diamine, as shown in Supplementary data. Free ligand of Mn5 was obtained as yellow-brown solids (yields 65% to 92%). 1H NMR (400 MHz, D2O) δH, ppm: 1.20 (9H, s, C(CH3)3), 1.22 (9H, s, C(CH3)3), 1.51-1.87 (8H, m, CH2), 2.41-2.51 (1H, m, CH), 2.52-2.61 (1H, m, CH), 7.60 (1H, d, J = 3.4 Hz, ArH), 7.74 (1H, d, J = 2 Hz, ArH), 7.77 (1H, d, J = 3.4 Hz, ArH), 7.82 (1H, d, J = 2 Hz, ArH), 8.28 (1H, s, ArCHN), 8.31 (1H, s, ArCHN). FT-IR (KBr) σ, cm-1: 3000-3700 (br, w, adsorbed water), 2933 (s, CH3), 2854 (s, CH2), 1600 (vs, CH=N), 1168 (s, anti-symmetric stretching of -SO3-), 1045 (vs, symmetric stretching of -SO3-). ESI-HRMS (negative, m/z): 196.3145 (Calcd. for [(M-4Na)+H]3- 196.2307) and 635.6009 (Calcd. for [(M-2Na)+H]- 635.6793). = -125 (c 0.01 g mL-1, H2O). Ideal formula of free ligand of Mn5 is C28H36N2O8S2Na4∙H2O. Anal. Calcd. for free ligand of Mn5: C, 47.9; H, 5.4; N, 3.9. Found: C, 47.7; H, 5.4; N, 3.8.

Mn5 was obtained as brown solids (yields 80% to 89% based on the mole of free ligand). FT-IR (KBr) σ, cm-1: 3430 (br, s, HO-H), 2952 and 2862 (both m, C-H on methyl), 1608 (s, C=N), 1403 (s, phenyl), 1119 (m, anti-symmetric stretching of –SO3-), 1066 (m, symmetric stretching of –SO3-), and 540 (w, Mn-O). = -192 (c 0.01 g mL-1, H2O). Ideal formula of catalyst Mn5 was C28H36N2O8S2Na2MnCl∙H2O. Anal. Calcd. for Mn5: C, 45.01; H, 5.09; N, 3.75. Found: C, 45.91; H, 5.95; N, 4.46. Mn3+ was 1.46 mmol g-1 determined by ICP-AES (1.34 mmol g-1 as ideal value based on formula).