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Paper | Regular issue | Vol 81, No. 11, 2010, pp.2479-2495
Published online, 3rd September, 2010
DOI: 10.3987/COM-10-11926
Computational Study on the Cyclopropanation Reaction of Ylides Generated from α-Pyridiniumacetates

Shuji Matsumura,* Ryukichi Takagi, Satoshi Kojima, Katsuo Ohkata, and Manabu Abe

*First Institute of New Drug Discovery Medicinal Chemistry Group, Otsuka Pharmaceutical Co., Ltd., 463-10 Kagasuno, Kawauchi-cho, Tokushima 771-0192,


Ab initio MO calculations were performed on the cyclopropanation reaction of methylidenemalononitriles with the ylide generated from α-pyridiniumacetates. The calculations indicated that the rate-determining step was the final cyclopropane forming step for the gas phase reaction, whereas solvent effect approximations implied that it was the initial Michael addition leading to the cis intermediate for reaction in water. It was also revealed that the plausible [3+2] cycloaddition reaction to give bicyclic products is more likely to be a stepwise and not an asynchronous concerted process in DFT calculations at the B3LYP/6-31G(d) level of theory.