Substituent effects on decarbonylation: Theoretical study of the interconversion of 1,2-bisketenes, cyclopropenones and alkynes

Kuangsen Sung, De Cai Fang, David Glenn, Thomas T. Tidwell

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16 引文 斯高帕斯(Scopus)

摘要

The structures and energies of the stationary points for decarbonylation of substituted 1,2-bisketenes 14 forming cyclopropenones 1 which further decarbonylate to alkynes 16 have been calculated by ab initio and hybrid B3LYP methods. At the HF/6-31G* level ketenylcarbene intermediates 15 are formed from 14 but at the MP2/6-31G* and B3LYP levels the conversion of 14 to 1 becomes a one-step process. Decarbonylation of bisketenes 14 is favored by electronegative substituents, but decarbonylation of cyclopropenones 1 to alkynes 16 is favored by electropositive substituents, in agreement with experimental results. The stabilization of cyclopropenones by π-donor substituents (NH2, OH and F) explains why OR and F, but not Me3Si, substituted cyclopropenones have been observed as products from bisketene photolyses.

原文English
頁(從 - 到)2073-2080
頁數8
期刊Journal of the Chemical Society. Perkin Transactions 2
發行號9
DOIs
出版狀態Published - 1998 九月

All Science Journal Classification (ASJC) codes

  • 化學 (全部)

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