Substituent effects on decarbonylation: theoretical study of the interconversion of 1,2-bisketenes, cyclopropenones and alkynes
作者： Kuangsen Sung , De-Cai Fang , David Glenn , Thomas T. Tidwell
DOI: 10.1039/A703912C
关键词:
摘要: The structures and energies of the stationary points for decarbonylation substituted 1,2-bisketenes 14 forming cyclopropenones 1 which further decarbonylate to alkynes 16 have been calculated by ab initio hybrid B3LYP methods. At HF/6-31G* level ketenylcarbene intermediates 15 are formed from 14, but at MP2/6-31G* levels conversion becomes a one-step process. Decarbonylation bisketenes is favored electronegative substituents, electropositive in agreement with experimental results. stabilization π-donor substituents (NH2, OH F) explains why OR F, not Me3Si, observed as products bisketene photolyses.
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