Formic Acid → (1S,3S)-3-[(tert-Butoxycarbonyl)amino]cyclopentyl formate

反応式

N(C(OCC)=O)=N[C:3](OCC)=[O:4].[CH3:13][C:14]([O:17][C:18](=[O:26])[NH:19][C@H:20]1[CH2:24][CH2:23][C@@H:22]([OH:25])[CH2:21]1)([CH3:16])[CH3:15].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(O)=O>>[CH3:16][C:14]([O:17][C:18](=[O:26])[NH:19][C@H:20]1[CH2:24][CH2:23][C@H:22]([O:25][CH:3]=[O:4])[CH2:21]1)([CH3:13])[CH3:15]

参加物

反応物 4

HCID 284Formic Acid

HCID 11776Triphenylphosphine

HCID 220568ethyl N-ethoxycarbonyliminocarbamate

HCID 216370811,1-Dimethylethyl N-((1S,3R)-3-hydroxycyclopentyl)carbamate

生成物 1

HCID 86754023(1S,3S)-3-[(tert-Butoxycarbonyl)amino]cyclopentyl formate収率 50.1%

実験手順

Diethyl azodicarboxylate (0.164 ml, 1.23 mmol) was added dropwise to a stirred solution of (1S-cis)-(3-hydroxycyclopentyl)carbamic acid 1,1-dimethylethyl ester (0.124 g, 0.61 mmol), triphenylphosphine (0.323 g, 1.23 mmol) and formic acid (0.046 ml, 1.23 mmol) and the solution was stirred at room temperature for 2h. The solution was then concentrated and purified by column chromatography on flash silica eluting with 10-30% ethyl acetate in cyclohexane to give the title compound (0.07 g) as white needles from diisopropyl ether m.p.84-85° C., [α]D -12.7° (CHCl3 c=0.55%).