The Aza-Morita-Baylis-Hillman Reaction: A Mechanistic and Kinetic Study

被引：22

作者：

Lindner, Christoph ^{[1
]}

Liu, Yinghao ^{[1
]}

Karaghiosoff, Konstantin ^{[1
]}

Maryasin, Boris ^{[1
]}

Zipse, Hendrik ^{[1
]}

机构：

[1] Ludwig Maximilians Univ Munchen, Dept Chem, D-81377 Munich, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2013年 / 19卷 / 20期

关键词：

kinetics; Lewis bases; NMR spectroscopy; reaction mechanisms; solvent effects; synthetic methods; N-SULFONATED IMINES; METHYL VINYL KETONE; LEWIS-BASE ORGANOCATALYST; CHIRAL BRONSTED ACIDS; ACTIVATED OLEFINS; HILIMAN REACTION; BIFUNCTIONAL ORGANOCATALYSTS; CARBONYL-COMPOUNDS; PHENYL ACRYLATE; ALDEHYDES;

D O I：

10.1002/chem.201204006

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The aza-Morita-BaylisHillman (aza-MBH) reaction has been studied in a variety of solvents, a selection of imine substrates and with various combinations of PPh3 and para-nitrophenol as the catalyst system. The measured kinetic data indicates that the effects of solvent and protic co-catalyst are strongly interdependent. These results are most easily reconciled with a mechanistic model involving the reversible protonation of zwitterionic intermediates in the catalytic cycle, which is also supported by 31PNMR spectroscopy and quantum chemical studies.

引用

页码：6429 / 6434

页数：6

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