A stepwise mechanism for the uncatalyzed michael addition of acetylacetone to methyl vinyl ketone

被引：3

作者：

Deuri, Sanjib ^{[1
]}

Phukan, Prodeep ^{[1
]}

机构：

[1] Gauhati Univ, Dept Chem, Gauhati 781001, Assam, India

来源：

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY | 2012年 / 112卷 / 03期

关键词：

Michael addition; stepwise mechanism; MP2; reactivity descriptor; methyl vinyl ketone; acetylacetone; IONIC LIQUID; 1,3-DICARBONYL COMPOUNDS; DENSITY; SOLVENT; CATALYST;

D O I：

10.1002/qua.23064

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A stepwise mechanism for the uncatalyzed Michael addition of acetylacetone (AcAc) to methyl vinyl ketone (MVK) has been studied by ab initio calculations at the MP2/6-31+G (d, p)// B3LYP/6-31+G (d, p) level of theory. This stepwise mechanism is initiated by a DielsAlder-type attack of MVK on the double bond of the cis-enol of AcAc followed by cleavage of the cycloadduct and proton transfer leading to the formal Michael adduct. Nature of interaction between AcAc and MVK has been probed using reactivity descriptors defined within the context of conceptual DFT. This stepwise mechanism is found to have a low barrier than the concerted mechanism proposed earlier. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011

引用

页码：801 / 808

页数：8

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