Takahashi Hideki, Hossain Kabir M, Nishihara Yasushi, Shibata Takanori, Takagi Kentaro
Department of Chemistry, Faculty of Science, Okayama University, Tsushima, Okayama 700-8530, Japan.
J Org Chem. 2006 Jan 20;71(2):671-5. doi: 10.1021/jo0520994.
[reaction: see text] The catalytic activity of a Rh complex in cross-coupling between ArZnI and TMSCH2I was examined in which the Rh complex, generated in situ from [RhCl(1,5-cyclooctadiene)]2 and 1,1'-bis(diphenylphosphino)ferrocene, exhibited excellent catalytic activity for the production of various functionalized benzylsilanes in good yields. From 31P NMR studies of various solutions containing several of the reaction components, confirmation of the rapid and quantitative transfer of aryl groups from ArZnI to the Rh complex to form arylrhodium species was ascertained. A catalytic cycle, commencing with the transmetalation, was thus proposed for the reaction.
[反应:见正文] 研究了一种铑配合物在ArZnI与TMSCH2I交叉偶联反应中的催化活性,其中由[RhCl(1,5-环辛二烯)]2和1,1'-双(二苯基膦基)二茂铁原位生成的铑配合物对各种功能化苄基硅烷的制备表现出优异的催化活性,产率良好。通过对含有几种反应组分的各种溶液的31P NMR研究,确定了芳基从ArZnI快速定量转移到铑配合物以形成芳基铑物种。因此提出了一个从金属转移开始的催化循环用于该反应。