Dimethylformamide → rel-(1S,2R,5S)-2-azido-5-(tert-butyl(diphenyl)silyl)oxy-1-methyl-cyclopentanol

HRID 245065Notes

Reaction equation

[C:1]([Si:5]([O:18][C@@H:19]1[C@:24]2([CH3:25])[C@@H:22]([O:23]2)[CH2:21][CH2:20]1)([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)([CH3:4])([CH3:3])[CH3:2].[N-:26]=[N+:27]=[N-:28].[Na+].CN(C=O)C.Cl([O-])(=O)(=O)=O.[Li+]>O>[N:26]([C@@H:22]1[CH2:21][CH2:20][C@H:19]([O:18][Si:5]([C:1]([CH3:2])([CH3:4])[CH3:3])([C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=2)[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C@@:24]1([CH3:25])[OH:23])=[N+:27]=[N-:28]

Participants

Conditions

Temperature: 60 °C

Procedure

A mixture of rel-tert-butyl-[[(1S,4S,5S)-5-methyl-6-oxabicyclo[3.1.0]hexan-4-yl]oxy]-diphenyl-silane (enantiomeric mixture) (1.0 g, 2.8 mmoles), sodium azide (782 mg, 11.9 mmol), and DMF (10 mL) is stirred at 60° C. for 16 h. Lithium perchlorate (604 mg, 5.7 mmol) and additional sodium azide (931 mg, 14.2 mmol) are added and the reaction is heated to 90° C. for 72 h, then cooled to room temperature. The reaction is treated with water (50 mL) and extracted with EtOAc (3×70 mL). The combined organic portions are dried over magnesium sulfate, filtered, and concentrated to afford the title compound as a pale yellow oil (2.51 g). The material is carried forward crude without further purification or characterization.

Workup

temperaturethe reaction is heated to 90° C. for 72 h
temperaturecooled to room temperature
extractionextracted with EtOAc (3×70 mL)
dry with materialThe combined organic portions are dried over magnesium sulfate
filtrationfiltered
concentrationconcentrated

Sources & evidence

ORD record: ord-4f179355917b4a18beed25f93d2bfbcd
Source dataset: uspto-grants-2014_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08658693B2

Reaction notes

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