Trimethylamine oxide dihydrate → (2-Hydroxy-2-hydroxymethyl-6,6-dimethyl-bicyclo[3.1.1]hept-3-ylmethyl)-carbamic acid benzyl ester

HRID 1420798Notes

Reaction equation

HRID 1420798 reaction equation
[CH2:1]([O:8][C:9](=[O:22])[NH:10][CH2:11][CH:12]1[CH2:17][CH:16]2[CH2:18][CH:14]([C:15]2([CH3:20])[CH3:19])[C:13]1=[CH2:21])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH2:23].[OH2:24].C[N+]([O-])(C)C>C(Cl)Cl.[Os](=O)(=O)(=O)=O>[CH2:1]([O:8][C:9](=[O:22])[NH:10][CH2:11][CH:12]1[CH2:17][CH:16]2[CH2:18][CH:14]([C:15]2([CH3:19])[CH3:20])[C:13]1([OH:24])[CH2:21][OH:23])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 198430Trimethylamine oxide dihydrateHCID 54031778(6,6-Dimethyl-2-methylene-bicyclo[3.1.1]hept-3-ylmethyl)-carbamic acid benzyl ester

Product 1

HCID 54267394(2-Hydroxy-2-hydroxymethyl-6,6-dimethyl-bicyclo[3.1.1]hept-3-ylmethyl)-carbamic acid benzyl esterYield 61.9%

Reagents, catalysts & solvents 2

HCID 30318Osmium TetroxideCatalystHCID 6344DichloromethaneSolvent

Procedure

(6,6-Dimethyl-2-methylene-bicyclo[3.1.1]hept-3-ylmethyl)-carbamic acid benzyl ester (2.19 g, 7.32 mmol), prepared in step B of example 47, was dissolved in CH2Cl2 (50 ml). To this solution was added trimethylamine N-oxide dihydrate (894 mg, 8.79 mmol) and osmium tetroxide (136 mg, 0.535 mmol). The solution was stirred at ambient temperature for 16 hours after which time the reaction was concentrated under vacuum and chromatographed on silica gel using a gradient starting with 30% ethyl acetate in hexanes to 50% ethyl acetate in hexanes to give 1.51 g of the titled compound as a brown oil: C.I. m/z 316 [M+1-H2 0]; 1H NMR (CDCl3)δ 7.31-7.39 (m, 5H), 5.59 (br s, 1H), 5.12 (s, 2H), 3.30-3.58 (m, 4H), 1.93-2.28 (m, 4H), 1.52 (m, 1H), 1.24-1.30 (m, 5H), 0.96 (s, 3H).

Workup

  1. concentrationwas concentrated under vacuum
  2. customchromatographed on silica gel using a gradient

Sources & evidence

ORD record
ord-67255f7892c3480f81e17c548f411c9d
Source dataset
uspto-grants-2000_06
Patent number
US06071935

Reaction notes

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