kulinkovich reaction crl反应.pdfVIP

J. Am. Chem. Soc. 2001, 123, 5777 A Theoretical Study on the Mechanism and Diastereoselectivity of the Kulinkovich Hydroxycyclopropanation Reaction Yun-Dong Wu* and Zhi-Xiang Yu Contribution from the Department of Chemistry, The Hong Kong Uniersity of Science Technology, Clear Water Bay, Kowloon, Hong Kong, China Recei ed January 12, 2001 Abstract: A detailed mechanism for the Kulinkovich hydroxycyclopropanation reaction has been explored with density functional theory calculations on the reactions between R1 2 1 COOMe and Ti(OMe) (CH CHR ) (R 2 2 and R2 are hydrogen and alkyl groups). Addition of ester to titanacyclopropane is found to be fast, exothermic, and irreversible. It has a preference for the -addition manifold over the -addition manifold in which its cycloinsertion transition states suffer from the steric repulsion between the R2 and ester. The following intramolecular methoxy migration step is also exothermic with reasonable activation energy. The cyclopropane- 1 2 forming step is the rate-determining step, which affords the experimentally observed cis-R /R diastereoselectivity in the -addition manifold b