[(3R,5R)-3,5-Bis[(tert-butyldimethylsilyl)oxy]-1-hydroxy4-methylenecyclohexyl]methanol → (3R,5R)-3,5-Bis[(tert-butyldimethylsilyl)oxy]4-methylenecyclohexanone

HRID 1862202Notes

Reaction equation

I([O-])(=O)(=O)=O.[Na+].[Si:7]([O:14][C@H:15]1[C:20](=[CH2:21])[C@H:19]([O:22][Si:23]([C:26]([CH3:29])([CH3:28])[CH3:27])([CH3:25])[CH3:24])[CH2:18][C:17](CO)([OH:30])[CH2:16]1)([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8]>CO.[Cl-].[Na+].O>[Si:7]([O:14][C@H:15]1[C:20](=[CH2:21])[C@H:19]([O:22][Si:23]([C:26]([CH3:29])([CH3:28])[CH3:27])([CH3:25])[CH3:24])[CH2:18][C:17](=[O:30])[CH2:16]1)([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8]

Participants

Conditions

Temperature: 0 °C

Procedure

Sodium periodate saturated water (2.2 mL) was added to a solution of the diol 4 (146 mg, 0.36 mmol) in methanol (9 mL) at 0° C. The solution was stirred at 0° C. for 1 h, poured into brine and extracted with ether and benzene. The organic extracts were combined, washed with brine, dried (MgSO4) and evaporated. An oily residue was dissolved in hexane (1 mL) and applied on a silica Sep-Pak cartridge. Pure 4-methylenecyclohexanone derivative 5 (110 mg, 82%) was eluted with hexane/ethyl acetate (95:5) as a colorless oil: 1H NMR (CDCl3) δ 0.050 and 0.069 (6H and 6H, each s, 4× SiCH3), 0.881 (18H, s, 2× Si-t-Bu), 2.45 (2H, ddd, J=14.2, 6.9, 1.4 Hz), 2.64 (2H, ddd, J=14.2, 4.6, 1.4 Hz), 4.69 (2H, dd, J=6.9, 4.6 Hz), 5.16 (2H, s); MS m/z (relative intensity) no M+, 355 (M+-Me, 3), 313 (M+-t-Bu, 100), 73 (76).

Workup

extractionextracted with ether and benzene
washwashed with brine
dry with materialdried (MgSO4)
customevaporated
dissolutionAn oily residue was dissolved in hexane (1 mL)
washPure 4-methylenecyclohexanone derivative 5 (110 mg, 82%) was eluted with hexane/ethyl acetate (95:5) as a colorless oil

Sources & evidence

ORD record: ord-3c6c8b1c08524a13a2ee3da6f9e0e8db
Source dataset: uspto-grants-2003_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06537981B2

Reaction notes

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