Supplementary Electronic Information

Catalytic Alkaline Oxidation of Lignin and its Model Compounds: a Pathway to Aromatic Biochemicals

Ali Azarpira,a John Ralph,a,bFachuang Lu*a,b

aGreat Lakes Bioenergy Research Center, Wisconsin Energy Institute, University of Wisconsin, Madison, WI, USA

bDepartment of Biochemistry, University of Wisconsin, Madison, WI, USA

Fig. S1 Yield data from non-catalytic oxidation of (a) compound 1 at 0.27 MPa (40 psi) O2 (data from Table S2); and catalytic oxidation of (b) compound 1 at 1.24 MPa (180 psi) O2 (data from Table S3), (c) compound 2 at 0.27 MPa (40 psi) O2 (data from Table S4), (d) 1a at 1.24 MPa (180 psi) O2 (Data from Table S6),(e)1b at 1.24 MPa (180 psi) O2 (data from Table S7), (f)2a at 1.24 MPa (180 psi) O2 (data from Table S8), (g)2b at 1.24 MPa (180 psi) O2 (data from Table S9).Compound numbers same as in Fig. 2

Fig. S2 Proposed structures for the new oxidized G΄-related units based on tentative NMR assignments

Time (h) / Yield (%)
1 / 1a / 1b / 1c
1.0 / 60.7 / 0.3 / 20.5 / 21.9
2.0 / 40.1 / 0.8 / 30.3 / 30.6
3.5 / 17.8 / 1.4 / 42.7 / 35.7
5.3 / 10.4 / 1.5 / 51.9 / 28.4
8.3 / 5.9 / 1.7 / 53.4 / 4.7
13.0 / 5.0 / 1.0 / 52.9 / 0.0
18.0 / 4.2 / 1.1 / 52.0 / 0.0
20.0 / 3.1 / 0.7 / 50.7 / 0.0

Table S1. Catalytic oxidation yields of compound 1 at 0.27 MPa (40 psi) O2 (Fig.3a). Compound numbers same as in Fig. 2

Time (h) / Yield (%)
1 / 1a / 1b / 1c
1.0 / 94.0 / 0.0 / 0.2 / 3.8
3.0 / 83.9 / 0.0 / 0.4 / 11.1
6.5 / 64.8 / 0.0 / 0.7 / 22.0
12.0 / 44.0 / 0.0 / 0.9 / 28.0
20.0 / 24.7 / 0.0 / 1.0 / 31.8

Table S2. Non-catalytic oxidation yields of compound 1 at 0.27 MPa (40 psi) O2 (Fig.S1a). Compound numbers same as in Fig. 2

Time (h) / Yield (%)
1 / 1a / 1b / 1c
0.3 / 65.3 / 0.1 / 2.7 / 8.9
1.0 / 30.0 / 0.4 / 5.7 / 16.7
1.7 / 13.3 / 0.6 / 7.6 / 13.8
2.3 / 2.4 / 0.8 / 7.5 / 6.9
3.0 / 0.0 / 0.9 / 7.5 / 2.9

Table S3. Catalytic oxidation yields of compound 1 at 1.24 MPa (180 psi) O2 (Fig.S1b). Compound numbers same as in Fig. 2

Time (h) / Yield (%)
2 / 2a / 2b / 1c
4.0 / 87.4 / 10.0 / 1.1 / 2.6
7.0 / 71.8 / 18.0 / 2.1 / 3.8
12.0 / 50.0 / 30.0 / 2.0 / 3.9
17.0 / 35.0 / 39.0 / 2.0 / 2.0
24.0 / 24.7 / 50.2 / 2.2 / 0.0

Table S4. Catalytic oxidation yields of compound 2 at 0.27 MPa (40 psi) O2 (Fig.3b). Compound numbers same as in Fig. 2

Time (h) / Yield (%)
2 / 2a / 2b / 1c
2.5 / 74.0 / 15.5 / 7.2 / 0
4.7 / 47.1 / 32.8 / 11.8 / 0
9.0 / 19.0 / 52.0 / 7.0 / 0
12.0 / 8.3 / 60.5 / 6.1 / 0
18.0 / 5.0 / 65.0 / 5.0 / 0
24.0 / 2.6 / 67.6 / 3.4 / 0

Table S5. Catalytic oxidation yields of compound 2 at 1.24 MPa (180 psi) O2 (Fig.S1c). Compound numbers same as in Fig. 2

Time (h) / Yield (%)
1a
0.5 / 90.0
1.0 / 73.0
1.5 / 61.0
2.5 / 45.0
4.5 / 23.0
7.0 / 10.0
10.0 / 0.0

Table S6. Catalytic oxidation yields of 1a at 1.24 MPa (180 psi) O2 (Fig.S1d). Compound numbers same as in Fig. 2

Time (h) / Yield (%)
1a / 1b
2.0 / 0.3 / 93.0
4.5 / 0.1 / 83.0
10.0 / 0.1 / 59.0
15.0 / 0.0 / 40.0
21.0 / 0.0 / 19.7
24.0 / 0.0 / 13.5

Table S7. Catalytic oxidation yields of 1b at 1.24 MPa (180 psi) O2 (Fig.S1e). Compound numbers same as in Fig. 2

Time (h) / Yield (%)
2a
3.0 / 99.6
7.5 / 98.2
11.0 / 97.0
16.0 / 95.0
21.0 / 91.4
24.0 / 84.3

Table S8. Catalytic oxidation yields of 2a at 1.24 MPa (180 psi) O2 (Fig.S1f). Compound numbers same as in Fig. 2

Time (h) / Yield (%)
2a / 2b
3.0 / 2.6 / 95.2
7.5 / 6.2 / 85.1
11.0 / 8.8 / 79.1
16.0 / 13.0 / 70.0
21.0 / 15.5 / 63.6
24.0 / 17.4 / 59.6

Table S9. Catalytic oxidation yields of 2b at 1.24 MPa (180 psi) O2 (Fig.S1g). Compound numbers same as in Fig. 2

Time (h) / Yield (%)
1a / 1b
3 / 2.6 / 10.7
8 / 2.5 / 12.5
12 / 2.5 / 13.7
16 / 1.9 / 13.4
18 / 1.7 / 13.1
21 / 1.6 / 12.9
24 / 1.4 / 12.8

Table S10. Catalytic oxidation of compound 3 at 0.27 MPa (40 psi) O2 (Fig.3c). Compound numbers same as in Fig. 2

Time (h) / Yield (%)
1a / 1b
2 / 1.2 / 5.1
5 / 2.1 / 7.6
9 / 2.6 / 9.5
15 / 3.0 / 11.0
24 / 3.5 / 12.6

Table S11. Catalytic oxidation of compound 4 at 0.27 MPa (40 psi) O2 (Fig. 3d). Compound numbers same as in Fig. 2

1