Oxygen → (3R)-2,2-Dimethyl-4-oxo-3-(1,1,2,2-tetramethyl-1-silapropoxy)butyl (3-chloropropyl)sulfonate

HRID 1671417Notes

Reaction equation

HRID 1671417 reaction equation
[Cl:1][CH2:2][CH2:3][CH2:4][S:5]([O:8][CH2:9][C:10]([CH3:27])([CH3:26])[C@@H:11]([O:18][Si:19]([CH3:25])([CH3:24])[C:20]([CH3:23])([CH3:22])[CH3:21])/[CH:12]=C/C(OC)=O)(=[O:7])=[O:6].O=O.[O:30]=[O+][O-].CSC>ClCCl>[Cl:1][CH2:2][CH2:3][CH2:4][S:5]([O:8][CH2:9][C:10]([CH3:26])([CH3:27])[C@@H:11]([O:18][Si:19]([CH3:25])([CH3:24])[C:20]([CH3:22])([CH3:21])[CH3:23])[CH:12]=[O:30])(=[O:6])=[O:7]

Participants

6

Reactant 4

HCID 977OxygenHCID 1068Dimethyl SulfideHCID 24823OzoneHCID 86628874Methyl (2E)(4S)-6-[(3-chloropropyl)sulfonyloxy]-5,5-dimethyl-4-(1,1,2,2-tetramethyl-1-silapropoxy)hex-2-enoate

Product 1

HCID 86628875(3R)-2,2-Dimethyl-4-oxo-3-(1,1,2,2-tetramethyl-1-silapropoxy)butyl (3-chloropropyl)sulfonateYield 52%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Following the general procedure for the preparation of aldehydes from alkenes of Description 11, methyl (2E)(4S)-6-[(3-chloropropyl)sulfonyloxy]-5,5-dimethyl-4-(1,1,2,2-tetramethyl-1-silapropoxy)hex-2-enoate (15a) (2.4 g, 5.4 mmol) dissolved in 25 mL of dichloromethane (DCM) was treated with a mixture of oxygen and ozone (O2/O3). Upon completion of the reaction, 2 mL (1.59 g, 27.2 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=1:3) as eluent to provide 1.1 g (52% yield) of the title compound (15b) as a colorless oil. Rf=0.75 (EtOAc/Hxn=1:2). 1H NMR (400 MHz, CDCl3): δ=0.07 (s, 3H), 0.10 (s, 3H), 0.96 (s, 9H), 1.06 (s, 3H), 1.09 (s, 3H), 2.30-2.37 (m, 2H), 3.28-3.32 (m, 2H), 3.69-3.73 (m, 3H), 4.01 (d, J=9.6 Hz, 1H), 4.12 (d, J=9.6 Hz, 1H), 9.62 (d, J=2.4 Hz, 1H) ppm. MS (ESI) m/z 409.13 (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=1:3) as eluent

Sources & evidence

ORD record
ord-ff230cce9b4d4a0c929c551c8e0bd044
Source dataset
uspto-grants-2011_08
Patent number
US07994218B2

Reaction notes

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