Triphenylphosphine → HCID 86638107, compound

HRID 655518Notes

Reaction equation

HRID 655518 reaction equation
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.[CH2:34]([O:36][C:37](=[O:52])[CH2:38][CH2:39][N:40]([C:45]([O:47][C:48]([CH3:51])([CH3:50])[CH3:49])=[O:46])[C@H:41]([CH3:44])[CH2:42]O)[CH3:35].[N-:53]=[N+:54]=[N-:55]>O1CCCC1>[CH2:34]([O:36][C:37](=[O:52])[CH2:38][CH2:39][N:40]([C:45]([O:47][C:48]([CH3:51])([CH3:50])[CH3:49])=[O:46])[C@H:41]([CH3:44])[CH2:42][N:53]=[N+:54]=[N-:55])[CH3:35]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 33558AzideHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 86638106HCID 86638106, compound

Product 1

HCID 86638107HCID 86638107, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Triphenylphosphine (12.0 g, 45.9 mmol) and diisopropyl azodicarboxylate (9.88 g, 45.9 mmol) were added at room temperature to a solution of 3-[tert-butoxycarbonyl-((R)-2-hydroxy-1-methyl-ethyl)-amino]-propionic acid ethyl ester in tetrahydrofuran (600 ml), then after 2 min diphenylphorphoryl azide (12.6 g, 45.9 mmol) was added. After 16 h the reaction mixture was concentrated and the residue purified by chromatography (SiO2; heptane-ethyl acetate gradient) to afford slightly impure 3-[tert-butoxycarbonyl-((R)-2-azido-1-methyl-ethyl)-amino]-propionic acid ethyl ester (8.82 g). This was dissolved in methanol (880 ml), then after addition of palladium (10% on activated charcoal, 1.6 g) and potassium carbonate (42.6 g, 308 mmol) the reaction mixture was hydrogenated at room temperature and atmospheric pressure for 16 h. Insoluble material was removed by filtration and the filtrate concentrated. Chromatography (SiO2; heptane/ethyl acetate 1:1, then dichloromethane/methanol/25% aq. ammonia solution 97.5:2.5:0.25) produced the title compound (2.20 g, 21%). White solid, MS (ISP)=229.4 (M+H)+.

Workup

  1. concentrationAfter 16 h the reaction mixture was concentrated
  2. customthe residue purified by chromatography (SiO2; heptane-ethyl acetate gradient)

Sources & evidence

ORD record
ord-e3373e86871c40f6bcaf12f9897d3fdf
Source dataset
uspto-grants-2011_12
Patent number
US08071586B2

Reaction notes

Loading…