Ieki Ryosuke, Kani Yuria, Tsunoi Shinji, Shibata Ikuya
Research Center for Environmental Preservation, Osaka University, 2-4 Yamadaoka, Suita, Osaka 565-0871 (Japan).
Chemistry. 2015 Apr 13;21(16):6295-300. doi: 10.1002/chem.201406496. Epub 2015 Mar 5.
Donor-acceptor cyclopropanes are useful building blocks for catalytic cycloaddition reactions with a range of electrophiles to give various cyclic products. In contrast, relatively few methods are available for the synthesis of homoallylic alcohols through coupling of vinylcyclopropanes (VCPs) with aldehydes, even with transition-metal catalysts. Here, we report that the hydrostannation of vinylcyclopropanes (VCPs) was effectively promoted by dibutyliodotin hydride (Bu2 SnIH). The resultant allylic tin compounds reacted easily with aldehydes. Furthermore, the use of Bu2 SnIH was effectively catalytic in the presence of hydrosilane as a hydride source, which established a coupling reaction of VCPs with aldehydes for the synthesis of homoallylic alcohols without the use of transition-metal catalysts. In contrast to conventional catalytic reactions of VCPs, the presented method allowed the use of several VCPs in addition to conventional donor-acceptor cyclopropanes.
供体-受体环丙烷是用于与一系列亲电试剂进行催化环加成反应以生成各种环状产物的有用结构单元。相比之下，即使使用过渡金属催化剂，通过乙烯基环丙烷（VCPs）与醛的偶联来合成高烯丙醇的方法也相对较少。在此，我们报道二丁基碘化锡氢化物（Bu2SnIH）能有效促进乙烯基环丙烷（VCPs）的氢化锡化反应。生成的烯丙基锡化合物能轻松与醛反应。此外，在硅烷作为氢化物源存在的情况下，Bu2SnIH具有有效的催化作用，这建立了VCPs与醛的偶联反应，用于在不使用过渡金属催化剂的情况下合成高烯丙醇。与传统的VCPs催化反应不同，所提出的方法除了传统的供体-受体环丙烷外，还允许使用几种VCPs。
