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Efficient Generation and Synthetic Applications of Alkyl-Substituted Siloxycarbenes: Suppression of Norrish-Type Fragmentations of Alkanoylsilanes by Triplet Energy Transfer.
Chemistry - A European Journal ( IF 4.3 ) Pub Date : 2019-11-08 , DOI: 10.1002/chem.201904635
Kento Ishida 1 , Hokuto Yamazaki 1 , Chihiro Hagiwara 1 , Manabu Abe 2 , Hiroyuki Kusama 1
Affiliation  

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.

中文翻译:

烷基取代的甲硅烷碳烯的高效生成和合成应用:通过三重态能量转移抑制烷酰基硅烷的Norrish型断裂。

已知酰基硅烷在光辐照下会异构化为甲硅烷碳烯,因此生成的碳烯可以用于各种合成反应。但是这种卡宾的形成不一定对某些链烷酰基硅烷有效,因为诺里斯型断裂竞争,这限制了链烷酰基硅烷作为卡宾前体的合成效用。在这项研究中,通过使用Ir络合物[Ir {dF(CF3)ppy} 2(dtbpy)] PF6考察了由可见光诱导的能量转移从烷酰基硅烷生成甲硅烷碳烯,并将其成功应用于CC偶联反应与硼酸酯或醛。这种方法有效地抑制了不良的诺里斯型反应,并拓宽了烷酰基硅烷的合成效用。
更新日期:2020-01-23
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