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

HRID 1455875
Notes
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Reaction equation

HRID 1455875 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]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 2

HCID 10787320[(3R,5R)-3,5-Bis[(tert-butyldimethylsilyl)oxy]-1-hydroxy4-methylenecyclohexyl]methanolHCID 23667635Sodium periodate

Product 1

HCID 10690562(3R,5R)-3,5-Bis[(tert-butyldimethylsilyl)oxy]4-methylenecyclohexanone

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 57417360Sodium chloride; water
Solvent

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

  1. extractionextracted with ether and benzene
  2. washwashed with brine
  3. dry with materialdried (MgSO4)
  4. customevaporated
  5. dissolutionAn oily residue was dissolved in hexane (1 mL)
  6. 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-f3b8cc62642c4e13b5dfbef73903fb73
Source dataset
uspto-grants-1998_12
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05843928

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes