Mechanistic Study on Rh‐Catalyzed Stereoselective CC/CH Activation of tert‐Cyclobutanols. Issue 13 (24th February 2014)

• Record Type: Journal Article
• Authors: Yu, Haizhu; Wang, Chen; Yang, Yimeng; Dang, Zhi‐Min
• Is Part Of: Chemistry. Volume 20:Issue 13(2014)
• Page Start: 3839
• Page End: 3848
• Publication Date: 2014-02-24
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201303249
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>A mechanistic study was performed on the Rh‐catalyzed stereoselective CC/CH activation of <italic>tert</italic>‐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.</p> </abstract>