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论文类型：期刊论文

发表时间：2014-07-28

发表刊物：ORGANOMETALLICS

收录刊物：SCIE、EI、Scopus

卷号：33

期号：14

页面范围：3840-3846

ISSN号：0276-7333

摘要：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.