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钯(II)催化的烯丙醇与乙烯基醚的不对称偶联:对钯铜双金属催化剂的深入了解。

Palladium(II)-catalyzed asymmetric coupling of allylic alcohols and vinyl ethers: insight into the palladium and copper bimetallic catalyst.

作者信息

Kawamura Yasufumi, Kawano Yasuhiro, Matsuda Tomohiro, Ishitobi Yûta, Hosokawa Takahiro

机构信息

Department of Environmental Systems Engineering, Kochi University of Technology, 185 Miyanokuchi, Tosayamada, Kami-City, Kochi 782-8502, Japan.

出版信息

J Org Chem. 2009 Apr 17;74(8):3048-53. doi: 10.1021/jo802807w.

Abstract

The use of PdX(2), CuX(2) (X = OAc, OCOCF(3), or Cl), and catechol together with (S,S)-4,4'-bisbenzyl-2,2'-bioxazoline under O(2) induces the asymmetric coupling of cinnamyl alcohols and vinyl ethers to give (R)-(+)-2-alkoxy-4-benzylidenetetrahydrofurans in 40-53% ee (79% yield). The present study provides implications for the so-called Wacker catalyst of PdX(2) and CuX(2), in terms of that the anionic ligands (X) of Pd and Cu interchange between two metals.

摘要

在氧气存在下,将PdX₂、CuX₂(X = OAc、OCOCF₃或Cl)与邻苯二酚以及(S,S)-4,4'-双苄基-2,2'-二恶唑啉一起使用,可诱导肉桂醇和乙烯基醚发生不对称偶联,生成对映体过量值为40 - 53%(产率79%)的(R)-(+)-2-烷氧基-4-亚苄基四氢呋喃。本研究就PdX₂和CuX₂所谓的瓦克催化剂而言提供了启示,即Pd和Cu的阴离子配体(X)在两种金属之间发生交换。

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