The reaction of nitroso oxides with olefins: Concerted or nonconcerted addition?

被引：0
作者：
M. R. Talipov
S. L. Khursan
R. L. Safiullin
机构：
[1] Russian Academy of Sciences,Institute of Organic Chemistry, Ufa Scientific Center
来源：
Russian Journal of Physical Chemistry A | 2011年 / 85卷
关键词：
nitroso oxides; olefins; cycloaddition; biradical addition; multi-reference self-consistent field methods;
D O I：
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中图分类号：
学科分类号：
摘要：
The mechanism of the interaction of nitroso oxides (RNOO) with olefins was studied at MCQDPT2/6-311+G(3df, 2p)//CASSCF(10; 9)/6-311G(d) level of theory. The following reaction channels were considered: (1) (3 + 2)-cycloaddition and nonconcerted biradical addition of nitroso oxide (2) through the terminal oxygen atom and (3) through the nitrogen atom to the C=C multiple bond. It was shown for the cases of (A) cis/trans-HNOO + C2H4, (B) cis/trans-HNOO + C2F4, (C) cis/trans-PhNOO + C2H4, and (D) cis/trans-PhNOO + C2H3CH3 model systems that the typical reaction of nitroso oxides with alkenes was cycloaddition. For olefins with a decreased electron density at the multiple bond, as in system B, a substantial contribution of the one-center mechanism with the formation of biradical intermediates is possible.
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页码：364 / 376
页数：12
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