Department of Chemistry, University of Rochester, Rochester, New York 14627-0216, United States.
Org Lett. 2011 May 20;13(10):2766-9. doi: 10.1021/ol200881v. Epub 2011 Apr 14.
A new method is presented for tandem reductive conjugate addition and silyl enol ether formation from cyclic and acyclic enones and enals in the presence of a Mn reductant, a Ni(terpyridine) catalyst, and a trialkylchlorosilane. The addition of secondary, tertiary, and hindered primary haloalkanes is demonstrated. Preliminary studies on the mechanism show that the intermediacy of L1(Ni)(η(3)-1-triethylsilyloxyalkenyl)X or in-situ-formed RMnX is unlikely.
本文提出了一种新的方法，即在 Mn 还原剂、Ni（三联吡啶）催化剂和三烷基氯硅烷的存在下，从环状和非环状烯酮和烯醛中进行串联还原共轭加成和硅烯醇醚形成。该方法还展示了仲、叔和位阻伯卤代烷的加成。对反应机理的初步研究表明，L1（Ni）（η（3）-1-三乙氧基硅基烯基）X 或原位形成的 RMnX 中间体不太可能存在。
