First Base-Free Catalytic Wittig Reaction

被引:67
|
作者
Schirmer, Marie-Luis [1 ]
Adomeit, Sven [1 ]
Werner, Thomas [1 ]
机构
[1] Leibniz Inst Katalyse eV, D-18059 Rostock, Germany
关键词
ORGANIC-SYNTHESIS; OXIDE REDUCTION; ONE-POT; OLEFINATION; MECHANISM; ALKENES; YLIDES; APPEL; ACID; HECK;
D O I
10.1021/acs.orglett.5b01352
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The first base-free catalytic Wittig reaction utilizing readily available Bu3P (5 mol %) as an organocatalyst is reported. The initial Michael addition of the phosphine to a suitable acceptor substituted alkene ultimately results in the formation of an ylide which is subsequently converted with an aldehyde. The presented H-1 NMR studies actually reveal evidence for the Michael addition and proposed ylide formation. Under the optimized reaction conditions various maleates and fumarates were converted with aromatic, heteroaromatic, and aliphatic aldehydes to evaluate the scope and limitations of this unprecedented reaction. Notably, maleates and fumarates react in a stereoconvergent fashion. The corresponding products were obtained in up to 95% isolated yield and E/Z-selectivities up to 99:1.
引用
收藏
页码:3078 / 3081
页数:4
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