Triphenylphosphine → HCID 88230228, compound

HRID 1596612Notes

Reaction equation

HRID 1596612 reaction equation
[Cl:1][C:2]1([Cl:13])[C@@H:4]([C:5]2[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=2)[C@@H:3]1[CH2:11]O.[C:14]([O:18][C:19]([NH:21][O:22][C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])=[O:20])([CH3:17])([CH3:16])[CH3:15].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1(C)C=CC=CC=1>[C:14]([O:18][C:19]([N:21]([CH2:11][C@H:3]1[C@H:4]([C:5]2[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=2)[C:2]1([Cl:13])[Cl:1])[O:22][C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])=[O:20])([CH3:17])([CH3:16])[CH3:15]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 2728863tert-Butyl (((1,1-dimethylethoxy)carbonyl)oxy)carbamateHCID 12524118HCID 12524118, compound

Product 1

HCID 88230228HCID 88230228, compoundYield 94%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Conditions

Temperature
-42 °C

Procedure

A solution of KOH (3.36 g, 60 mmol) and the product of Step 1, above, (10.36 g, 40 mmol) in a mixture of methanol (30 ml), tetrahydrofuran (30 ml) and water (90 ml) was stirred for 3 hours at room temperature. The reaction mixture was neutralized with 1N aqueous hydrochloric acid and extracted with diethyl ether (100 ml+2×50 ml). The combined organic phases were washed with saturated aqueous sodium bicarbonate (2×50 ml) and brine (50 ml), then dried over MgSO4. Evaporation of the solvent afforded (2,2-dichloro-trans-3-phenylcyclopropyl)methanol in quantitative yield. To a stirred solution of the alcohol thus prepared (4.34 g, 20 mmol), N,O-di-tert-butoxycarbonylhydroxylamine (5.83 g, 25 mmol), and triphenylphosphine (6.56 g, 25 mmol) in toluene (40 ml), cooled to −42° C. was added dropwise a solution of diethyl azodicarboxylate (4.35 g, 25 mmol) in toluene (5 ml) over 15 minutes under a nitrogen atmosphere. The reaction mixture was allowed to warm to room temperature overnight, insolubles were removed by filtration and the filtrate concentrated under reduced pressure. The resultant residue was purified by column chromatography (SiO2, 300 g; 8% ethyl acetate in n-hexane) affording the title compound (8.09 g, 94% yield).

Workup

  1. temperatureto warm to room temperature overnight
  2. custominsolubles were removed by filtration
  3. concentrationthe filtrate concentrated under reduced pressure
  4. customThe resultant residue was purified by column chromatography (SiO2, 300 g; 8% ethyl acetate in n-hexane)

Sources & evidence

ORD record
ord-fdcbe30a845747449438be1d52fdc644
Source dataset
uspto-grants-2001_09
Patent number
US06291520B1

Reaction notes

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