Release Time:2019-03-09  Hits:

Indexed by: Journal Article

Date of Publication: 2014-07-28

Journal: ORGANOMETALLICS

Included Journals: Scopus、EI、SCIE

Volume: 33

Issue: 14

Page Number: 3840-3846

ISSN: 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.