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Synfacts 2013; 9(1): 0040
DOI: 10.1055/s-0032-1317884
Synthesis of Materials and Unnatural Products
© Georg Thieme Verlag Stuttgart · New York

Intermolecular Reactions of Gold–Vinylidene Complexes

Contributor(s):
Timothy M. Swager
,
Gregory D. Gutierrez
Hashmi AS. K, * Wieteck M, Braun I, Rudolph M, Rominger F. Ruprecht-Karls-Universität Heidelberg, Germany
Gold Vinylidene Complexes: Intermolecular C(sp3)–H Insertions and Cyclopropanations Pathways.

Angew. Chem. Int. Ed. 2012;
51: 10633-10637
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Publication History

Publication Date:
17 December 2012 (online)

 
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Key words

gold–vinylidene complexes - intermolecular C–H insertion - benzocyclobutenes

Significance

This communication reports the application of gold–vinylidene complexes in intermolecular C(sp3)–H insertion reactions and cyclobutene syntheses. Vinylidene complex II is accessed via dual activation of the dialkyne starting material. In the presence of a cycloalkane, the authors found that II follows a C(sp3)–H insertion pathway to form the corresponding cycloalkylated products. However, the complex undergoes cyclopropanation with an alkene to eventually generate the benzocyclobutene derivative shown.


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Comment

The authors comment on the high stereoselectivity of the conversion of the dialkyne into benzocyclobutene, particularly noting that the stereochemical configuration of the alkenes used is cleanly reflected in the product. Additional experiments whose results are in favor of a stereospecific cyclopropanation pathway are discussed along with a proposed mechanism of the process.


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