α,β-不饱和醛高效两步转化为光学活性γ-氧基-α,β-不饱和腈及其在(+)-帕图洛内酯C全合成中的应用。
Efficient two-step conversion of alpha,beta-unsaturated aldehydes to optically active gamma-oxy-alpha,beta-unsaturated nitriles and its application to the total synthesis of (+)-patulolide C.
作者信息
Tian Jun, Yamagiwa Noriyuki, Matsunaga Shigeki, Shibasaki Masakatsu
机构信息
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
出版信息
Org Lett. 2003 Aug 21;5(17):3021-4. doi: 10.1021/ol034944f.
[reaction: see text] An efficient two-step conversion of alpha,beta-unsaturated aldehydes into optically active gamma-oxy-alpha,beta-unsaturated nitriles is described. First, catalytic asymmetric cyanation-ethoxycarbonylation using (S)-YLi(3)tris(binaphthoxide) (YLB) afforded chiral allylic cyanohydrin carbonate. Second, a [3,3]-sigmatropic rearrangement proceeded without racemization under thermal conditions to give gamma-oxy-alpha,beta-unsaturated nitriles. Lewis acids were also effective for the rearrangement, and the reaction proceeded smoothly under mild conditions. To demonstrate the utility of the conversion, concise catalytic enantioselective total synthesis of (+)-patulolide C was performed.
[反应：见正文] 描述了一种将α,β-不饱和醛高效两步转化为光学活性γ-氧基-α,β-不饱和腈的方法。首先，使用(S)-YLi(3)三(联萘酚盐)（YLB）进行催化不对称氰化-乙氧基羰基化反应，得到手性烯丙基氰醇碳酸酯。其次，[3,3]-σ迁移重排在热条件下进行且无消旋化，生成γ-氧基-α,β-不饱和腈。路易斯酸对该重排反应也有效，且反应在温和条件下顺利进行。为证明该转化方法的实用性，进行了(+)-patulolide C的简洁催化对映选择性全合成。
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