Efficient Generation and Synthetic Applications of Alkyl-Substituted Siloxycarbenes: Suppression of Norrish-Type Fragmentations of Alkanoylsilanes by Triplet Energy Transfer |
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| Authors: | Dr Kento Ishida Hokuto Yamazaki Chihiro Hagiwara Prof Dr Manabu Abe Prof Dr Hiroyuki Kusama |
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| Institution: | 1. Department of Chemistry, Faculty of Science, Gakushuin University, 1-5-1 Mejiro, Toshima-ku, Tokyo, 171-8588 Japan;2. Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526 Japan |
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| Abstract: | Acylsilanes have been known to undergo isomerization to siloxycarbenes under photoirradiation and the thus generated carbenes can be utilized for various synthetic reactions. But this carbene formation is not necessarily efficient with some alkanoylsilanes because Norrish-type fragmentations compete, which limit the synthetic utility of alkanoylsilanes as carbene precursors. In this study, generation of siloxycarbenes from alkanoylsilanes by visible-light-induced energy transfer was examined by using an Ir complex, Ir{dF(CF3)ppy}2(dtbpy)]PF6, and was successfully applied to the C−C coupling reactions with boronic esters or aldehydes. This methodology efficiently suppressed undesired Norrish-type reactions and broadened synthetic utility of alkanoylsilanes. |
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| Keywords: | acylsilanes energy transfer photochemistry siloxycarbenes triplet sensitizer |
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