Diisopropylamine → ethyl 9-benzyloxy-5(S)-tert-butoxycarbonylamino-4(R,S)-hydroxy-7,7-dimethyl-non-2-inoate

HRID 863274ノート

反応式

HRID 863274 の反応式
C([Li])CCC.C(NC(C)C)(C)C.[C:13]([O:17][CH2:18][CH3:19])(=[O:16])[C:14]#[CH:15].[CH2:20]([O:27][CH2:28][CH2:29][C:30]([CH3:44])([CH3:43])[CH2:31][C@H:32]([NH:35][C:36]([O:38][C:39]([CH3:42])([CH3:41])[CH3:40])=[O:37])[CH:33]=[O:34])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>CCCCCC.O1CCCC1>[CH2:20]([O:27][CH2:28][CH2:29][C:30]([CH3:44])([CH3:43])[CH2:31][C@H:32]([NH:35][C:36]([O:38][C:39]([CH3:42])([CH3:41])[CH3:40])=[O:37])[CH:33]([OH:34])[C:15]#[C:14][C:13]([O:17][CH2:18][CH3:19])=[O:16])[C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1

参加物

7

反応物 4

HCID 7912DiisopropylamineHCID 12182Ethyl propiolateHCID 228825796-Benzyloxy-2(S)-tert-butoxycarbonylamino-4,4-dimethyl-hexanalHCID 178418339Butyllithium

生成物 1

HCID 131720520ethyl 9-benzyloxy-5(S)-tert-butoxycarbonylamino-4(R,S)-hydroxy-7,7-dimethyl-non-2-inoate

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒3 回HCID 8058Hexane溶媒

実験手順

22.2 ml of a 1.6M n-butyllithium solution in hexane are added to a solution of 5.1 ml of diisopropylamine in 40 ml of tetrahydrofuran at -78° C. under argon, while stirring. After 30 min, a solution, cooled to -78° C., of 2.5 ml of ethyl propiolate in 20 ml of tetrahydrofuran is added dropwise via a cannula. The yellow reaction solution is stirred at -78° C. for a further 1 h and 5.0 g of 6-benzyloxy-2(S)-tert-butoxycarbonylamino-4,4-dimethyl-hexanal (Example 390) in 30 ml of tetrahydrofuran are then added dropwise. After the mixture has been stirred for 4.5 h, the reaction is quenched by addition of saturated aqueous ammonium chloride solution and the reaction mixture is allowed to warm to room temperature and is worked up in the customary manner. The crude product is purified by FC over silica gel (eluting agent C). The title compound is obtained as a mixture of the 4(S) and 4(R) diastereomers in a ratio of about (5.4:1): Rf (C)=0.28; FAB-MS: (M+H)+ =448.

後処理

  1. additionis added dropwise via a cannula
  2. stirringThe yellow reaction solution is stirred at -78° C. for a further 1 h
  3. stirringAfter the mixture has been stirred for 4.5 h
  4. customthe reaction is quenched by addition of saturated aqueous ammonium chloride solution
  5. customThe crude product is purified by FC over silica gel (eluting agent C)

出典と根拠

ORDレコード
ord-81f4d465f5c34d4cbf1c34ae0b02a007
出典データセット
uspto-grants-1998_02
特許番号
US05719141

反応ノート

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