Triphenylphosphine → HCID 178418853, compound

HRID 916049Notes

Reaction equation

HRID 916049 reaction equation
[C:1]([O:5][C:6](=[O:15])[NH:7][C@H:8]1[CH2:13][CH2:12][C@H:11](O)[CH2:10][CH2:9]1)([CH3:4])([CH3:3])[CH3:2].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.N(C(OCC)=O)=NC(OCC)=O.C1(P([N:61]=[N+:62]=[N-:63])(C2C=CC=CC=2)=O)C=CC=CC=1>C1COCC1>[C:1]([O:5][C:6](=[O:15])[NH:7][C@H:8]1[CH2:13][CH2:12][C@@H:11]([N:61]=[N+:62]=[N-:63])[CH2:10][CH2:9]1)([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 199401P,P-Diphenylphosphinic azideHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 178418329HCID 178418329, compound

Product 1

HCID 178418853HCID 178418853, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-10 °C

Procedure

To a cooled (−10° C.) and stirred solution under Ar of (trans-4-hydroxy-cyclohexyl)carbamic acid tert-butyl ester (10.0 g) (H. Noguchi, T. Aoyama, T. Shioiri, Heterocycles 2002, 58, 471-504) and PPh3 (18.3 g) in THF (250 ml) was added diethyl azodicarboxylate (12.1 g). After 5 min a solution of diphenylphosphoryl azide (19.2 g) in THF (250 ml) was slowly added from a dropping funnel. The reaction mixture was stirred 6 h at −10° C. and stirring was continued over night at RT. After dilution with Et2O the mixture was washed with H2O. The aqueous layer was washed with one more portion of Et2O. The combined organic layers were dried over Na2SO4 and the solvent was evaporated. Chromatography (silica, CH2Cl2 to CH2Cl2/5% MeOH) afforded 12.0 g (quant.) of product still contaminated by side products. This material was used as this in the following step. Light yellow semisolid.

Workup

  1. stirringstirring
  2. waitwas continued over night at RT
  3. washAfter dilution with Et2O the mixture was washed with H2O
  4. washThe aqueous layer was washed with one more portion of Et2O
  5. dry with materialThe combined organic layers were dried over Na2SO4
  6. customthe solvent was evaporated
  7. customChromatography (silica, CH2Cl2 to CH2Cl2/5% MeOH) afforded 12.0 g (quant.) of product

Sources & evidence

ORD record
ord-ea0785edea5a40d6b7ba02893ea88566
Source dataset
uspto-grants-2007_09
Patent number
US07268154B2

Reaction notes

Loading…