Sodium borohydride → (1S,3R)-3-{[tert-Butyl(dimethyl)silyl]oxy}cyclopentan-1-ol

HRID 2561Notes

Reaction equation

HRID 2561 reaction equation
[Si:1]([O:8][C@@H:9]1[CH2:13][C@H:12]([OH:14])[CH:11]=[CH:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[BH4-].[Na+]>C(O)C.[Ni]>[Si:1]([O:8][C@@H:9]1[CH2:10][CH2:11][C@H:12]([OH:14])[CH2:13]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 4311764Sodium borohydrideHCID 101767472-Cyclopenten-1-ol, 4-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-, cis-

Product 1

HCID 54118351(1S,3R)-3-{[tert-Butyl(dimethyl)silyl]oxy}cyclopentan-1-olYield 87.3%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 702EthanolSolvent

Conditions

Temperature
0 °C

Procedure

Dissolve (-)-cis-4-tert-butyldimethylsilyloxy-2-cyclopentenol (28.85 g, 135 mmol, prepared in example 10) in ethanol (75 mL) and treated with Raney nickel (1.85 g, 32 mmol, previously washed with water (2×50 mL) and ethanol (2×50 mL)). Charge the atmosphere with hydrogen at 50 psi (344.74 kPa) and shake the mixture. After 5.25 hours, filter the reaction. Cool the filtrate to 0° C. and treat with sodium borohydride (0.54 g, 14.3 mmol). After stirring for 2 hours, concentrate the solution under vacuum and distill the resulting oil by Kugelrohr distillation (40°-60° C., 1 mmHg) to provide the title compound (25.5 g, 87%) as a colorless oil, [α]20 =-3.9°, (c=0.99, chloroform); 1H NMR (CDCl3) δ4.4 (m, 1H), 4.3 (m, 1H), 3.03 (d, 1H, J=10.5 Hz), 1.9-1.6 (m, 6H), 0.89 (s, 9H), 0.07 (s, 6H); 13C NMR (CDCl3) δ74.9, 74.1, 44.4, 34.2, 34.1, 25.8, 17.9, -4.9, -5.0; IR (neat) νmax 3405, 2957, 2932, 2888, 2858, 1256, 1091, 1069, 1038, 1026 cm-1 ; CIMS m/e (% relative intensity) 217 (M+H+ 81), 199 (M+H+ --H2O, 37) 67 (100). This (-)-enantiomer (title compound) could not be separated from the (+)-enantiomer (antipode) using the previously described chiral column.

Workup

  1. washpreviously washed with water (2×50 mL) and ethanol (2×50 mL))
  2. additionCharge the atmosphere with hydrogen at 50 psi (344.74 kPa) and shake the mixture
  3. filtrationfilter
  4. customthe reaction
  5. concentrationconcentrate the solution under vacuum
  6. distillationdistill the resulting oil
  7. distillationby Kugelrohr distillation (40°-60° C., 1 mmHg)

Sources & evidence

ORD record
ord-8055ba3e80dd4839935a05e583536aad
Source dataset
uspto-grants-1998_03
Patent number
US05728899

Reaction notes

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