Triphenylphosphine → ({(1S,2S,4R)-4-azido-2-[(benzyloxy)methyl]cyclopentyl}-oxy)(tert-butyl)dimethylsilane

HRID 447611Notes

Reaction equation

HRID 447611 reaction equation
[CH2:1]([O:8][CH2:9][C@H:10]1[C@@H:14]([O:15][Si:16]([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17])[CH2:13][C@@H:12](O)[CH2:11]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCOC(/N=N/C(OCC)=O)=O.C1C=CC(OP(OC2C=CC=CC=2)([N:64]=[N+:65]=[N-:66])=O)=CC=1>C1COCC1>[N:64]([C@H:12]1[CH2:13][C@H:14]([O:15][Si:16]([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17])[C@H:10]([CH2:9][O:8][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[CH2:11]1)=[N+:65]=[N-:66]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 123414Diphenylphosphoryl azideHCID 5462977Diethyl azodicarboxylateHCID 66798092(1S,3S,4S)-3-[(benzyloxy)methyl]-4-{[tert-butyl(dimethyl)silyl]oxy}cyclopentanol

Product 1

HCID 86618712({(1S,2S,4R)-4-azido-2-[(benzyloxy)methyl]cyclopentyl}-oxy)(tert-butyl)dimethylsilaneYield 63%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (1S,3S,4S)-3-[(benzyloxy)methyl]-4-{[tert-butyl(dimethyl)-silyl]oxy}cyclopentanol (138.9 mg, 0.0004127 mol) and PPh3 (118 mg, 0.000451 mol) in THF (2.7 mL) at 0° C. was slowly added DEAD (71.1 μL, 0.000451 mol). The reaction was stirred for 5 minutes, then diphenylphosphonic azide (97.4 μL, 0.000452 mol) was added dropwise. The mixture was stirred for one hour. The reaction was partitioned with water and EtOAc. The layers were separated and the aqueous extracted with EtOAc (2×). The combined organics were washed with brine (1×), dried (Na2SO4), filtered, and collected in vacuo. The residue was purified by flash chromatography (0 to 10% EtOAc/hexanes) to obtain 93.5 mg (63%) of the title compound.

Workup

  1. customat 0° C.
  2. stirringThe mixture was stirred for one hour
  3. customThe reaction was partitioned with water and EtOAc
  4. customThe layers were separated
  5. extractionthe aqueous extracted with EtOAc (2×)
  6. washThe combined organics were washed with brine (1×)
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. customcollected in vacuo
  10. customThe residue was purified by flash chromatography (0 to 10% EtOAc/hexanes)

Sources & evidence

ORD record
ord-c99a47b8ec5e4e46a847373595e83ca4
Source dataset
uspto-grants-2013_07
Patent number
US08481550B2

Reaction notes

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