Triphenylphosphine → Tert-butyl 9-bromo-2,3-dihydrobenzo[F][1,4]oxazepine-4(5H)-carboxylate

HRID 1514253Notes

Reaction equation

[Br:1][C:2]1[C:3]([OH:20])=[C:4]([CH2:8][N:9]([CH2:17][CH2:18]O)[C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[CH:5]=[CH:6][CH:7]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>O1CCCC1>[Br:1][C:2]1[C:3]2[O:20][CH2:18][CH2:17][N:9]([C:10]([O:11][C:12]([CH3:13])([CH3:14])[CH3:15])=[O:16])[CH2:8][C:4]=2[CH:5]=[CH:6][CH:7]=1

Participants

Conditions

Temperature: 0 °C

Procedure

A mixture of 1,1-dimethylethyl [(3-bromo-2-hydroxyphenyl)methyl](2-hydroxyethyl)carbamate (Preparation 100) (2.35 g, 6.79 mmol) and triphenylphosphine (1.96 g, 7.47 mmol) in tetrahydrofuran (40 ml) under nitrogen was cooled to 0° C. Diisopropyl azodicarboxylate (DIAD) (1.47 ml, 7.47 mmol) was added dropwise and the resulting mixture stirred for 1 h then concentrated in vacuo. The solvent was removed and the material washed twice with brine, dried (magnesium sulphate) then concentrated in vacuo. Purification of the residue by flash chromatography on silica gel, eluting with 5-25% ethyl acetate in cyclohexane gave the title compound (1.35 g). MS (ES) C14H1879BrNO2 requires 327 found 228 [M+H—COOC(CH3)3]+.

Workup

concentrationthen concentrated in vacuo
customThe solvent was removed
washthe material washed twice with brine
dry with materialdried (magnesium sulphate)
concentrationthen concentrated in vacuo
customPurification of the residue by flash chromatography on silica gel
washeluting with 5-25% ethyl acetate in cyclohexane

Sources & evidence

ORD record: ord-c7485fb9cde640faacb3d82faa899e5b
Source dataset: uspto-grants-2012_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08222245B2

Reaction notes

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