Photochemically Promoted Transition Metal-Free Cross-Coupling of Acylsilanes with Organoboronic Esters
Photochemically Promoted Transition Metal-Free Cross-Coupling of Acylsilanes with Organoboronic Esters
复制标题
DOI：
10.1021/ja1102597
复制
发表时间：
2011-03-23
影响因子：
15
通讯作者：
Kusama, Hiroyuki
中科院分区：
文献类型：
--
作者：
Ito, Kazuta;Tamashima, Hiroto;Kusama, Hiroyuki
在几乎中性、无过渡金属的条件下，通过光照射实现了酰基硅烷和有机硼酸酯之间的分子间碳-碳键形成。在该反应中，酰基硅烷光异构化生成的环状卡宾与硼酸酯反应生成B-C键插入中间体，后者经过独特的重排反应生成环状α-烷氧基硼酸酯。在空气中对所得粗产物进行酸处理，以良好的产率提供交叉偶联酮。
Intermolecular carbon-carbon bond formation between acylsilanes and organoboronic esters was achieved by photoirradiation under almost neutral, transition metal-free conditions. In this reaction, siloxycarbenes generated by photoisomerization of acylsilanes reacted with boronic esters to give the formal B-C bond insertion intermediates, which underwent unique rearrangement to afford the cyclic alpha-alkoxyboronic esters. Acidic treatment of the resulting crude products under air furnished the cross-coupled ketones in good yields.