Triphenylphosphine → Cis-1-azido-2-methyl-cyclohexane

HRID 2235202Notes

Reaction equation

[CH3:1][C@@H:2]1[CH2:7][CH2:6][CH2:5][CH2:4][C@H:3]1O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.C1(P([N:54]=[N+:55]=[N-:56])(C2C=CC=CC=2)=O)C=CC=CC=1>C1COCC1.O>[N:54]([C@@H:3]1[CH2:4][CH2:5][CH2:6][CH2:7][C@@H:2]1[CH3:1])=[N+:55]=[N-:56]

Participants

Conditions

Temperature: -20 °C

Procedure

Dissolve trans-2-methyl-cyclohexanol (5.0 g, 44.0 mmol) in anhydrous THF (500 mL) and cool to −20° C. Add triphenylphosphine (57.43 g, 218.9 mmol), diethyl azodicarboxylate (38.13 g, 218.9 mmol), and diphenylphosphoryl azide (60.25 g, 218.9 mmol) respectively under nitrogen. Stir the reaction mixture for 6 hours at the same temperature then warm it to room temperature and stir overnight Add water (500 mL), and extract the aqueous layer with EtOAc (3×500 mL). Combine the organic layers and dry with Na2SO4, filter, concentrate and purify by flash column chromatography (silica gel, 0-25% of EtOAc/Hexane) to give 3.98 g (65%) of the title compound as a colorless oil: 1H NMR (CDCl3) δ 3.08-3.16 (m, 1H), 1.90-1.98 (m, 1H), 1.56-1.78 (m, 3H), 1.16-1.35 (m, 4H), 1.01 (d, 3H), 0.93-1.03 (m, 1H).

Workup

temperaturethen warm it to room temperature
stirringstir overnight
extractionextract the aqueous layer with EtOAc (3×500 mL)
dry with materialCombine the organic layers and dry with Na2SO4
filtrationfilter
concentrationconcentrate
custompurify by flash column chromatography (silica gel, 0-25% of EtOAc/Hexane)

Sources & evidence

ORD record: ord-09ab59effcf347c0aa2fde19426bfa75
Source dataset: uspto-grants-2010_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07713979B2

Reaction notes

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