Zirconocene-Mediated Selective C-C Bond Cleavage of Strained Carbocycles: Scope and Mechanism

Citation:

Bruffaerts, J. ; Vasseur, A. ; Singh, S. ; Masarwa, A. ; Didier, D. ; Oskar, L. ; Perrin*, L. ; Eisenstein*, O. ; Marek*, I. Zirconocene-Mediated Selective C-C Bond Cleavage of Strained Carbocycles: Scope and Mechanism. The Journal of Organic Chemistry 2018.
Zirconocene-Mediated Selective C-C Bond Cleavage of Strained Carbocycles: Scope and Mechanism

Abstract:

Several approaches using organozirconocene species for the remote cleavage of strained three-membered ring carbocycles are described. -Ene polysubstituted cyclopropanes, alkylidenecyclopropanes, -ene spiro[2.2]pentanes and -ene cyclopropyl methyl ethers were successfully transformed into stereodefined organometallic intermediates allowing an easy access to highly stereoenriched acyclic scaffolds in good yields and in most cases excellent selectivities. DFT calculations and isotopic labeling experiments were performed to delineate the origin of the obtained chemo- and stereoselectivities, demonstrating the importance of microreversibility.

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Last updated on 03/18/2018