(1S,2R,4S,5R)-ethyl 4-hydroxy-1-methylbicyclo[3.1.0]hexane-2-carboxylate → (1S,2R,5R)-ethyl 1-methyl-4-oxobicyclo[3.1.0]hexane-2-carboxylate

HRID 2204467Notes

Reaction equation

HRID 2204467 reaction equation
[OH:1][C@H:2]1[C@@H:7]2[C@@:5]([CH3:8])([CH2:6]2)[C@@H:4]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH2:3]1.[OH:14][C@@H:15]1[C@H:20]2[C@:18]([CH3:21])([CH2:19]2)[C@H:17]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH2:16]1>>[CH3:8][C@@:5]12[CH2:6][C@@H:7]1[C:2](=[O:1])[CH2:3][C@@H:4]2[C:9]([O:11][CH2:12][CH3:13])=[O:10].[CH3:21][C@:18]12[CH2:19][C@H:20]1[C:15](=[O:14])[CH2:16][C@H:17]2[C:22]([O:24][CH2:25][CH3:26])=[O:23]

Participants

4

Reactant 2

HCID 58010081(1S,2R,4S,5R)-ethyl 4-hydroxy-1-methylbicyclo[3.1.0]hexane-2-carboxylateHCID 58010225(1R,2S,4R,5S)-ethyl 4-hydroxy-1-methylbicyclo[3.1.0]hexane-2-carboxylate

Product 2

HCID 58009781(1R,2S,5S)-ethyl 1-methyl-4-oxobicyclo[3.1.0]hexane-2-carboxylateHCID 58009803(1S,2R,5R)-ethyl 1-methyl-4-oxobicyclo[3.1.0]hexane-2-carboxylateYield 65%

Procedure

A mixture of (1R,2S,4R,5S)-ethyl 4-hydroxy-1-methylbicyclo[3.1.0]hexane-2-carboxylate and (1S,2R,4S,5R)-ethyl 4-hydroxy-1-methylbicyclo[3.1.0]hexane-2-carboxylate (0.59 g, 3.2 mmol) was subjected to General Procedure T to give (1R,2S,5S)-ethyl 1-methyl-4-oxobicyclo[3.1.0]hexane-2-carboxylate and (1S,2R,5R)-ethyl 1-methyl-4-oxobicyclo[3.1.0]hexane-2-carboxylate (0.38 g, 65%) after purification by silica gel chromatography eluting with a gradient of 20-50% EtOAc/pentane: 1H NMR (400 MHz, CDCl3) δ 4.35-4.15 (m, 2H), 3.12 (t, J=9.3 Hz, 1H), 2.60 (dd, J=9.2, 18.3 Hz, 1H), 2.37-2.23 (m, 1H), 1.68 (dd, J=3.4, 9.2 Hz, 1H), 1.48 (s, 3H), 1.41 (dd, J=3.4, 5.2 Hz, 1H), 1.34 (t, J=7.1 Hz, 3H), 1.14 (dd, J=5.3, 9.2 Hz, 1H).

Sources & evidence

ORD record
ord-136c1d527fbe486290b57110d25b00a4
Source dataset
uspto-grants-2016_06
Patent number
US09365579B2

Reaction notes

Loading…