Trost Barry M, Koester Dennis C, Herron Alastair N
Department of Chemistry, Stanford University, Stanford, CA 94305-5080 (USA).
Angew Chem Int Ed Engl. 2015 Dec 21;54(52):15863-6. doi: 10.1002/anie.201509238. Epub 2015 Nov 17.
The synthesis of vinyl boronates and vinyl silanes was achieved by employing a Ru-catalyzed alkene-alkyne coupling reaction of allyl boronates or allyl silanes with various alkynes. The double bond geometry in the generated vinyl boronates can be remotely controlled by the juxtaposing boron- and silicon groups on the alkyne substrate. The synthetic utility of the coupling products has been demonstrated in a variety of synthetic transformations, including iterative cross-coupling reactions, and a Chan-Lam-type allyloxylation followed by a Claisen rearrangement. A sequential one-pot alkene-alkyne-coupling/allylation-sequence with an aldehyde to deliver a highly complex α-silyl-β-hydroxy olefin with a handle for further functionalization was also realized.
通过钌催化烯丙基硼酸酯或烯丙基硅烷与各种炔烃的烯烃-炔烃偶联反应,实现了乙烯基硼酸酯和乙烯基硅烷的合成。生成的乙烯基硼酸酯中的双键几何构型可通过炔烃底物上相邻的硼和硅基团进行远程控制。偶联产物的合成效用已在各种合成转化中得到证明,包括迭代交叉偶联反应,以及Chan-Lam型烯丙氧基化反应,随后进行克莱森重排反应。还实现了与醛的连续一锅法烯烃-炔烃偶联/烯丙基化序列,以提供具有用于进一步功能化的手柄的高度复杂的α-硅基-β-羟基烯烃。