Journal of the American Chemical Society
Journal of the American Chemical Society
5 years ago

Structural Characterization and Unique Catalytic Performance of Silyl-Group-Substituted Geminal Dichromiomethane Complexes Stabilized with a Diamine Ligand

Structural Characterization and Unique Catalytic Performance of Silyl-Group-Substituted Geminal Dichromiomethane Complexes Stabilized with a Diamine Ligand
Toshiyuki Oshiki, Ryuji Taniguchi, Naoki Hosokawa, Masahito Murai, Hiroko Mimachi, Yusuke Nishida, Kazuhiko Takai
Stabilization by a silyl group on the methylene carbon and a diamine ligand led to the isolation of gem-dichromiomethane species. X-ray crystallography confirmed the identity of the structure of this rare example of reactive gem-dimetalloalkane species. The isolated gem-dichromiomethane complex acted as a storable silylmethylidene carbene equivalent, with reactivity that could be changed dramatically upon addition of a Lewis acid (ZnCl2) and a base (TMEDA) to promote both silylalkylidenation of polar aldehydes and silylcyclopropanation of nonpolar alkenes. Identification of a key reactive species also identified the catalytic version of these transformations and provided insights into the reaction mechanism. In contrast to Simmons–Smith cyclopropanation, the real reactive species for the current cyclopropanation was a chromiocarbene species, not a chromium carbenoid species.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b07487

DOI: 10.1021/jacs.7b07487

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