Table 4.
Desymmetrizations of substituted prochiral cycloketones 11–21a
| Structure | R | Comp. no | CAMO | OTEMO | Reference biotransformation | |||||
|---|---|---|---|---|---|---|---|---|---|---|
| Conv (%)a | ee (%)b | Conv (%)a | ee (%)b | Conv (%)a | ee (%)b | Biocatalyst | References | |||
|
3-Vinyl | 11 | 100 | 99(−) | 100 | 99(−) | n.a. | n.a. | n.a. | This work |
| Bn | 12 | 99 | 97(+) | 98 | 11(−) | +++ | 44(+) | HAPMO | [43] | |
| +++ | 93(−) | CHMOBrevi1 | ||||||||
| 3-(3-MeOBn) | 13 | 100 | 94(−) | 100 | 82(−) | +++ | 63(−) | CPMOComa | [43] | |
| 3-(4-MeOBn) | 14 | 95 | 95(+) | 100 | 64(+) | +++ | 24(+) | CPMOComa | [43] | |
| 3-(3,4,5-tri-MeOBn) | 15 | 100 | 92(+) | 87 | 63(+) | +++ | 79(+) | CHMOBrevi1 | [43] | |
|
Me | 16 | 100 | 99(−) | 100 | 58(+) | +++ | 99(−) | CDMO | [24] |
| +++ | 64(+) | CPMOComa | [44] | |||||||
| OH | 17 | 100 | >99(+) | n.a. | n.a. | +++ | 99(−) | CHMOXantho | [24] | |
| +++ | 44(+) | CHMOBrevi2 | ||||||||
| tBu | 18 | 98 | 77(−) | 100 | 98(+) | +++ | 99(−) | CPDMO | [18] | |
| COOEt | 19 | 99 | 95(−) | 57 | 96(+) | +++ | 99(−) | CPDMO | [18] | |
| +++ | 64(+) | CPMOComa | [18] | |||||||
|
H, H | 20 | 100 | 97(−) | 100 | 96(−) | +++ | 99(−) | CDMO | [24] |
| H, OH (trans) | 21 | 100 | 96(+) | 100 | 94(+) | +++ | 96(+) | CHMOAcineto | [45] | |
n.a. not applicable
aRelative conversion (Conv) of starting material determined by chiral phase GC after 24 h: +++>90%, ++50–90%, +<50%
bEnantiomeric excess values determined by chiral phase GC; sign of optical rotation is given in parenthesis and assigned on the basis of reference biotransformations