Oxygen → (3R)-2,2-Dimethyl-4-oxo-3-(phenylmethoxy)butyl (3-chloropropyl)sulfonate

HRID 1671408Notes

Reaction equation

HRID 1671408 reaction equation
[Cl:1][CH2:2][CH2:3][CH2:4][S:5]([O:8][CH2:9][C:10]([CH3:23])([CH3:22])[C@@H:11]([O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[CH:12]=C)(=[O:7])=[O:6].O=O.[O:26]=[O+][O-].CSC>ClCCl.C(O)C>[Cl:1][CH2:2][CH2:3][CH2:4][S:5]([O:8][CH2:9][C:10]([CH3:22])([CH3:23])[C@@H:11]([O:14][CH2:15][C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)[CH:12]=[O:26])(=[O:6])=[O:7]

Participants

7

Reactant 4

HCID 977OxygenHCID 1068Dimethyl SulfideHCID 24823OzoneHCID 86628869(3S)-2,2-Dimethyl-3-(phenylmethoxy)pent-4-enyl (3-chloropropyl)sulfonate

Product 1

HCID 86628868(3R)-2,2-Dimethyl-4-oxo-3-(phenylmethoxy)butyl (3-chloropropyl)sulfonateYield 60%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6344DichloromethaneSolvent

Procedure

Following the general procedure for the preparation of aldehydes from alkenes of Description 11, (3S)-2,2-dimethyl-3-(phenylmethoxy)pent-4-enyl (3-chloropropyl]sulfonate (11a) (25.0 g, 69.3 mmol) dissolved in a mixture of 300 mL of dichloromethane (DCM) and 40 mL of ethanol was treated with a mixture of oxygen and ozone (O2/O3). Upon completion of the reaction, 10.6 mL (9.0 g, 138 mmol) of dimethyl sulfide (DMS) was added. After work-up, the crude material was purified by silica gel column chromatography using a mixture of ethyl acetate (EtOAc) and hexane (Hxn) (EtOAc/Hxn=1:6) as eluent to provide 15.0 g (60% yield) of the title compound (11b) as a colorless oil. Rf=0.22 (EtOAc/Hxn=1:6). 1H NMR (400 MHz, CDCl3): δ=1.10 (s, 6H), 2.26-2.33 (m, 2H), 3.23-3.29 (m, 2H), 3.65 (d, J=2.8 Hz, 1H), 3.63-3.68 (m, 2H), 4.03 (d, J=9.6 Hz, 1H), 4.15 (d, J=8.8 Hz, 1H), 4.50 (d, J=11.2 Hz, 1H), 4.68 (d, J=11.2 Hz, 1H), 7.30-7.39 (m, 5H), 9.73 (d, J=2.8 Hz, 1H) ppm. MS (ESI) m/z 385.03 (M+Na)+. The analytical data was consistent with the proposed structure.

Workup

  1. additionwas added
  2. customAfter work-up, the crude material was purified by silica gel column chromatography
  3. additiona mixture of ethyl acetate (EtOAc) and hexane (Hxn) (EtOAc/Hxn=1:6) as eluent

Sources & evidence

ORD record
ord-35c92ad085974fb288a32f762f2195d9
Source dataset
uspto-grants-2011_08
Patent number
US07994218B2

Reaction notes

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