期刊
ACS OMEGA
卷 5, 期 6, 页码 2957-2966出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsomega.9b03902
关键词
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资金
- National Natural Science Foundation of China [21762043]
- Research Foundation for Advanced Talents in Xinjiang Province
- Fundamental Research Funds for the Central University [xjj2015064]
The title reaction is theoretically investigated in detail using density functional theory. Three possible routes starting from keto-or enol-type vinylcyclopropylketone are considered in this work. Results indicate that phosphine catalyst would first attack at the three-membered ring (C3 position) rather than the terminal of alkene (C1 position) in vinylcyclopropylketone. It is found that the two-stage mechanism would be responsible for the title reaction. The first stage is the S(N)2'-type ring-opening of the keto-type vinylcyclopropylketone with phosphine catalyst. After the proton-transfer tautomerisms in the zwitterionic intermediates, the second stage is associated with the 7-endo-trig S(N)2'-type ring closure of keto- or enol-type zwitterions to furnish seven-membered cyclic products and recover the catalyst. Moreover, it turns out that 7-endo-trig S(N)2'-type ring closure would be highly asynchronous and could be well described as an addition/elimination process where the ring closure already finishes before the cleavage of the C-P bond. Computational results provide a deep insight into experimental observations.
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