Benzyl Alcohol → benzyl (1S,2S,3S,5S)-2-(tert-butyldimethylsilyloxy)bicyclo[3.1.0]hexan-3-ylcarbamate

HRID 56405Notes

Reaction equation

HRID 56405 reaction equation
[Si:1]([O:8][C@@H:9]1[C@@H:14](C(O)=O)[CH2:13][C@H:12]2[C@@H:10]1[CH2:11]2)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C([N:20]([CH2:23]C)CC)C.[CH2:25]([OH:32])[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:40])C=CC=CC=1>C1(C)C=CC=CC=1.C(OCC)(=O)C>[Si:1]([O:8][C@@H:9]1[C@@H:14]([NH:20][C:23](=[O:40])[O:32][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH2:13][C@H:12]2[C@@H:10]1[CH2:11]2)([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:2])[CH3:3]

Participants

7

Reactant 4

HCID 244Benzyl AlcoholHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 67113050(1S,2S,3S,5S)-2-(tert-butyldimethylsilyloxy)bicyclo[3.1.0]hexane-3-carboxylic acid

Product 1

HCID 131736924benzyl (1S,2S,3S,5S)-2-(tert-butyldimethylsilyloxy)bicyclo[3.1.0]hexan-3-ylcarbamateYield 54%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of (1S,2S,3S,5S)-2-(tert-butyldimethylsilyloxy)bicyclo[3.1.0]hexane-3-carboxylic acid (4 g, 15.625 mmol), triethylamine (22 mL, 156 mmol) and benzyl alcohol (17 mL, 156 mmol) in toluene (50 mL) at room temperature was added diphenyl phosphoryl azide (33.7 mL, 156 mmol) dropwise, and the resulting mixture was stirred at 100° C. overnight. The reaction solution was cooled to room temperature, diluted with ethyl acetate (100 mL) and washed with water (3×50 mL) and brine (50 mL). The organic layer was dried over sodium sulfate, filtered and concentrated to afford a crude product, which was purified by silica gel column chromatography (ethyl acetate:petroleum ether=1:8) to afford the title compound (3.0 g, 54%) as a white solid. MS (ES+) C20H31NO3Si requires: 361, found: 362 [M+H]+.

Workup

  1. temperatureThe reaction solution was cooled to room temperature
  2. washwashed with water (3×50 mL) and brine (50 mL)
  3. dry with materialThe organic layer was dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto afford a crude product, which
  7. customwas purified by silica gel column chromatography (ethyl acetate:petroleum ether=1:8)

Sources & evidence

ORD record
ord-b7942a6b4fd24d8590ab9731a262d48e
Source dataset
uspto-grants-2016_09
Patent number
US09434700B2

Reaction notes

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