Triphenylphosphine → ((3S,6S)-6-azido-2-oxo-azepan-3-yl)-carbamic acid tert-butyl ester

HRID 2224031Notes

Reaction equation

HRID 2224031 reaction equation
[C:1]([O:5][C:6](=[O:17])[NH:7][C@H:8]1[CH2:14][CH2:13][C@@H:12](O)[CH2:11][NH:10][C:9]1=[O:16])([CH3:4])([CH3:3])[CH3:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.C1(P([N:63]=[N+:64]=[N-:65])(C2C=CC=CC=2)=O)C=CC=CC=1>C1COCC1>[C:1]([O:5][C:6](=[O:17])[NH:7][C@H:8]1[CH2:14][CH2:13][C@H:12]([N:63]=[N+:64]=[N-:65])[CH2:11][NH:10][C:9]1=[O:16])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 199401P,P-Diphenylphosphinic azideHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 11149222(3S,6R)-3-(tert-butoxycarbonyl)aminohexahydro-6-hydroxy-2H-azepin-2-one

Product 1

HCID 86609581((3S,6S)-6-azido-2-oxo-azepan-3-yl)-carbamic acid tert-butyl esterYield 70.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of ((3S,6R)-6-hydroxy-2-oxo-azepan-3-yl)carbamic acid tert-butyl ester (3 g, 12.3 mmol example 1 f) and triphenylphosphine (3.75 g, 14.1 mmol) in THF (200 mL) at 0° C. is added diethyl azodicarboxylate (2.2 mL, 13.5 mmol) at a rate to maintain a temperature <5° C. followed immediately by addition of diphenylphosphoryl azide (2.9 mL, 13.5 mmol). The reaction is stirred for 60 h at room temperature in the dark, the solvent is removed under vacuum and the residue chromatographed on silica (hexane to ether gradient) to give 2.33 g (70%) of ((3S,6S)-6-azido-2-oxo-azepan-3-yl)-carbamic acid tert-butyl ester as a solid. MS (ESI) 270 (M+H)+

Workup

  1. temperatureto maintain a temperature <5° C.
  2. customthe solvent is removed under vacuum
  3. customthe residue chromatographed on silica (hexane to ether gradient)

Sources & evidence

ORD record
ord-14f8f4dde41f4e28a2b04d1d49d8bdd9
Source dataset
uspto-grants-2008_05
Patent number
US07378410B2

Reaction notes

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