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Indexed by:期刊论文

Date of Publication:2014-07-28

Journal:ORGANOMETALLICS

Included Journals:SCIE、EI、Scopus

Volume:33

Issue:14

Page Number:3840-3846

ISSN No.:0276-7333

Abstract:Methyltrioxorhenium (MTO)-catalyzed transfer of a methylene group to styrene has been computationally found to preferably follow a stepwise mechanism to give phenylcyclopropane via formation of a pseudo-metallacyclic intermediate and subsequent alkylative cyclization. The present result serves as the first theoretical evidence for d(0) transition metal mediated transfer of methylene as a terminal form rather than a metal carbene or carbenoid fashion, accompanied by the cleavage of a H2C=O double bond. The mechanism presented here is in contrast to the carbenoid or metal carbene promoted methylene transfer and to the MTO-catalyzed isoelectronic atom (group) transfer in MeRe(O)(2)(eta(2)-O-NH) or MeRe(O)(2)(eta(2)-O-O). This study not only enriches the chemistry of olefin cyclopropanation and the MTO-catalyzed group (atom) transfer event but also sheds new light on the reaction chemistry of formaldehyde.