著者

福留 裕樹 畠山 琢次 原 賢二 中村 正治 中村 栄一

出版者

基礎有機化学会(基礎有機化学連合討論会)

雑誌

基礎有機化学討論会要旨集(基礎有機化学連合討論会予稿集)

巻号頁・発行日

vol.16, pp.1103, 2002

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Development of the stereocontrolled carbon-carbon bond formation is one of the most important tasks in synthetic organic chemistry. We have reported that a zincated hydrazone, which is a synthetic equivalent and an isoelectronic compound of a metal enolate, reacts with various vinyl metal compounds such as vinyl silane, vinyl stannane, and vinylmagnesium halide to form a new functionalized organometallics bearing two metals at the same carbon. We recently found that a vinyl boronate can also serve as the carbometalation acceptor and shows high reactivity toward organozinc reagents. Here we report an alkenyl boronate, which possesses a variety of substituent at the &beta;-carbon to boron, undergoes the addition of a zincated hydrazone in high yields with high diastereoselectivity. The zincated hydrazone derived from 2-methyl-3-pentanone hydrazone, thus, reacted with <I>trans-</i>hexenyl boronate to give a product in 92% yield with high diastereoselectivity (d.r. > 99:1). On the other hand, the reaction to the corresponding <I>cis-</i>isomer gave another diastereomer with a diastereoselectivity of 16:84, showing high stereospecificity of the carbozincation process.