Takeuchi Taiichi, Aoyama Tsukasa, Orihara Kurumi, Ishida Kento, Kusama Hiroyuki
Department of Chemistry, Faculty of Science, Gakushuin University, Tokyo 171-8588, Japan.
Org Lett. 2021 Dec 17;23(24):9490-9494. doi: 10.1021/acs.orglett.1c03683. Epub 2021 Nov 30.
A novel methodology for generation of Fischer-type metal-carbene complexes was developed. Photoirradiation to a mixture of an acylsilane and a cationic copper complex cleanly gave a Fischer-type copper-siloxycarbene complex, which was detected by spectroscopic methods. This carbene complex reacted with siloxydienes in a [4 + 1] cycloaddition manner to give cyclopentene derivatives. It is noteworthy that this reaction proceeds with a catalytic amount of copper through generation of a Fischer-type copper-siloxycarbene complex intermediate.
开发了一种生成费舍尔型金属卡宾配合物的新方法。对酰基硅烷和阳离子铜配合物的混合物进行光照射，可直接得到费舍尔型铜 - 硅氧基卡宾配合物，该配合物通过光谱方法检测到。这种卡宾配合物与硅氧基二烯以[4 + 1]环加成方式反应，生成环戊烯衍生物。值得注意的是，该反应通过生成费舍尔型铜 - 硅氧基卡宾配合物中间体，以催化量的铜进行。
