title: Mechanistic study on Rh-catalyzed stereoselective C-C/C-H activation of tert-cyclobutanols.
abstract: A mechanistic study was performed on the Rh-catalyzed stereoselective C-C/C-H activation of tert-cyclobutanols. The present study corroborated the previous proposal that the reaction occurs by metalation, β-C elimination, 1,4-Rh transfer, C=O insertion, and a final catalyst-regeneration step. The rate-determining step was found to be the 1,4-Rh transfer step, whereas the stereoselectivity-determining step did not correspond to any of the aforementioned steps. It was found that both the thermodynamic stability of the product of the β-C elimination and the kinetic feasibility of the 1,4-Rh transfer and C=O insertion steps made important contributions. In other words, three steps (i.e., β-C elimination, 1,4-Rh transfer, and C=O insertion) were found to be important in determining the configurations of the two quaternary stereocenters.
authors.affiliation: Department of Polymer Science and Engineering, University of Science and Technology Beijing, Beijing 100083 (P. R. China).
authors.forename: Haizhu
authors.initials: H
authors.lastname: Yu
authors.forename: Chen
authors.initials: C
authors.lastname: Wang
authors.forename: Yimeng
authors.initials: Y
authors.lastname: Yang
authors.forename: Zhi-Min
authors.initials: ZM
authors.lastname: Dang
keywords: CC activation; CH activation; density functional calculations; reaction mechanisms; rhodium