Department of Chemistry, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8551, Japan.
J Am Chem Soc. 2011 Mar 23;133(11):3716-9. doi: 10.1021/ja1102597. Epub 2011 Feb 23.
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 α-alkoxyboronic esters. Acidic treatment of the resulting crude products under air furnished the cross-coupled ketones in good yields.
通过在近中性、无过渡金属条件下的光辐照，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，由酰基硅烷光异构化生成的硅氧基卡宾与硼酸酯反应，生成了形式上的 B-C 键插入中间体，该中间体经历了独特的重排，得到了环状α-烷氧基硼酸酯。在空气中对所得粗产物进行酸性处理，以良好的收率得到了交叉偶联酮。
