Role of base assisted proton transfer in N-heterocyclic carbene-catalyzed intermolecular Stetter reaction

被引：13
|
作者：
Ajitha, Manjaly J. [1 ]
Suresh, Cherumuttathu H. [1 ]
机构：
[1] CSIR Natl Inst Interdisciplinary Sci & Technol, Inorgan & Theoret Chem Sect, Chem Sci & Technol Div, Trivandrum, Kerala, India
来源：
TETRAHEDRON LETTERS | 2013年 / 54卷 / 52期
关键词：
Organocatalysis; N-Heterocyclic carbene; Stetter reaction; Breslow intermediate; Density functional theory; HYDROACYLATION; ANNULATIONS; UMPOLUNG; STATES; ENALS;
D O I：
10.1016/j.tetlet.2013.10.116
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The mechanism of the NHC-catalyzed intermolecular Stetter reaction between benzaldehyde and cyclopropene has been investigated using the PCM-M062X/6-311++G(3df,2p)//M062X/6-31+G(d,p) level of DFT. Compared to the direct reaction, a substantial reduction in the activation free energy by 10.6-14.4 kcal/mol is observed when the reaction is performed in the presence of water, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The bases promote the proton transfer step of the reaction to yield the Breslow intermediate. An early concerted transition state has been located for the stereocontrolling C-C bond formation step (Delta G(#) = 26.6 kcal/mol) which is used to explain the diastereomeric ratio observed in the experiment. (C) 2013 Elsevier Ltd. All rights reserved.
引用
收藏
页码：7144 / 7146
页数：3
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