Metal-Free SN2′ Decarboxylative Rearrangement of β-Keto Esters

被引：4
|
作者：
Bizet, Vincent [1 ]
Lefebvre, Valerie [1 ]
Baudoux, Jerome [1 ]
Lasne, Marie-Claire [1 ]
Boulange, Agathe [2 ,3 ]
Leleu, Stephane [2 ,3 ]
Franck, Xavier [2 ,3 ]
Rouden, Jacques [1 ]
机构：
[1] Univ Caen, Lab Chim Mol & Thioorgan, Inst Normand Chim Mol Med & Macromol INC3N, CNRS,ENSICAEN, F-14050 Caen, France
[2] Univ Rouen, Inst Normand Chim Mol Med & Macromol INC3M, INSA Rouen, UMR,CNRS6014, F-76130 Mont St Aignan, France
[3] Univ Rouen, Inst Normand Chim Mol Med & Macromol INC3M, INSA Rouen, FR3038,COBRA, F-76130 Mont St Aignan, France
来源：
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2011年 / 2011卷 / 22期
关键词：
Nucleophilic substitution; Reaction mechanisms; Organocatalysis; Rearrangement; Decarboxylation; INTRAMOLECULAR CONJUGATE DISPLACEMENT; ASYMMETRIC ALLYLIC ALKYLATION; GAMMA-UNSATURATED ALCOHOLS; CARROLL REARRANGEMENT; STEREOCONTROLLED SYNTHESIS; CLAISEN REARRANGEMENT; ETHYL ACETOACETATE; MICHAEL REACTION; ORGANOCATALYST; ZINCOPHORIN;
D O I：
10.1002/ejoc.201100120
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
Treatment of 2-methoxycarbonyl- (or 3-cyano-)allyl acetoacetates with a tertiary amine or triphenylphosphane afforded alpha-methylene gamma-substituted delta-keto esters (or nitrile) in satisfactory yields. Various bases and nucleophiles were tested to elucidate the mechanism. The results of the study strongly suggest an intermolecular pathway involving a S(N)2'-decarboxylation-S(N)2' cascade.
引用
收藏
页码：4170 / 4175
页数：6
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