tert-butyl ((2R)-1-((((9H-fluoren-9-yl)methoxy)carbonyl)(2-(((tert-butyldimethylsilyl)oxy)methyl)-1-cyanoallyl)amino)but-3-en-2-yl)(benzyloxy)carbamate → (5R)-(9H-fluoren-9-yl)methyl 5-((benzyloxy)(tert-butoxycarbonyl)amino)-3-(((tert-butyldimethylsilyl)oxy)methyl)-2-cyano-5,6-dihydropyridine-1(2H)-carboxylate

HRID 627183ノート

反応式

HRID 627183 の反応式
[CH:1]1[C:13]2[CH:12]([CH2:14][O:15][C:16]([N:18]([CH:39]([C:51]#[N:52])[C:40]([CH2:42][O:43][Si:44]([C:47]([CH3:50])([CH3:49])[CH3:48])([CH3:46])[CH3:45])=C)[CH2:19][C@H:20]([N:23]([O:31][CH2:32][C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=3)[C:24](=[O:30])[O:25][C:26]([CH3:29])([CH3:28])[CH3:27])[CH:21]=C)=[O:17])[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1>C1(C)C=CC=CC=1.CC1C=C(C)C(N2C(=[Ru](Cl)(Cl)=CC3C=CC=CC=3OC(C)C)N(C3C(C)=CC(C)=CC=3C)CC2)=C(C)C=1>[CH2:32]([O:31][N:23]([C:24]([O:25][C:26]([CH3:29])([CH3:27])[CH3:28])=[O:30])[C@H:20]1[CH2:19][N:18]([C:16]([O:15][CH2:14][CH:12]2[C:13]3[CH:1]=[CH:2][CH:3]=[CH:4][C:5]=3[C:6]3[C:11]2=[CH:10][CH:9]=[CH:8][CH:7]=3)=[O:17])[CH:39]([C:51]#[N:52])[C:40]([CH2:42][O:43][Si:44]([C:47]([CH3:48])([CH3:49])[CH3:50])([CH3:46])[CH3:45])=[CH:21]1)[C:33]1[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=1

参加物

4

反応物 1

HCID 131735285tert-butyl ((2R)-1-((((9H-fluoren-9-yl)methoxy)carbonyl)(2-(((tert-butyldimethylsilyl)oxy)methyl)-1-cyanoallyl)amino)but-3-en-2-yl)(benzyloxy)carbamate2 回

生成物 1

HCID 89852280(5R)-(9H-fluoren-9-yl)methyl 5-((benzyloxy)(tert-butoxycarbonyl)amino)-3-(((tert-butyldimethylsilyl)oxy)methyl)-2-cyano-5,6-dihydropyridine-1(2H)-carboxylate収率 40.7%

試薬・触媒・溶媒 2

HCID 11763533(1,3-Bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene)(dichloro)((2-((propan-2-yl)oxy)phenyl)methylidene)ruthenium触媒HCID 1140Toluene溶媒

反応条件

温度
90 °C

実験手順

A solution of tert-butyl ((2R)-1-((((9H-fluoren-9-yl)methoxy)carbonyl)(2-(((tert-butyldimethylsilyl)oxy)methyl)-1-cyanoallyl)amino)but-3-en-2-yl)(benzyloxy)carbamate (Intermediate 159, 3.32 g, 4.59 mmol) in toluene (150 mL) was bubbled with nitrogen for 15 minutes. Hoveyda-Grubbs Catalyst 2nd Generation (0.288 g, 0.46 mmol) was added and the mixture was bubbled with nitrogen for an additional 15 minutes. The resulting solution was heated under nitrogen at 90° C. for 2 days. The reaction mixture was evaporated. The residue was purified on silica gel column (0-30% EtOAc/hexane) to afford the title compound (1.300 g, 40.7%) as a light brown film.

後処理

  1. customthe mixture was bubbled with nitrogen for an additional 15 minutes
  2. customThe reaction mixture was evaporated
  3. customThe residue was purified on silica gel column (0-30% EtOAc/hexane)

出典と根拠

ORDレコード
ord-68dec6a226e14fa3a45ed2414dbd41d0
出典データセット
uspto-grants-2016_04
特許番号
US09309245B2

反応ノート

読み込み中…