通过用二茂锆（氢）氯还原炔丙醇直接立体定向合成丙二烯。
Direct and stereospecific synthesis of allenes via reduction of propargylic alcohols with Cp2Zr(H)Cl.
作者信息
Pu Xiaotao, Ready Joseph M
机构信息
Department of Biochemistry, University of Texas Southwestern Medical Center, 5323 Harry Hines Boulevard, Dallas, Texas 75390, USA.
出版信息
J Am Chem Soc. 2008 Aug 20;130(33):10874-5. doi: 10.1021/ja8035527. Epub 2008 Jul 25.
Abstract
Allenes can be synthesized via the direct SN2' addition of hydride to propargylic alcohols. Previous examples of this approach, however, have involved harsh reaction conditions and have suffered from incomplete transfer of central chirality to axial chirality. Here we show that Cp2Zr(H)Cl can react with the zinc or magnesium alkoxides of propargylic alcohols to generate allenes in good yield and in high optical purity. Dialkyl-, alkyl-aryl-, and diaryl-allenes are accessible by this method. Furthermore, the reaction can provide silyl-substituted allenes, trisubstituted allenes, and terminal allenes.
摘要
丙二烯可通过氢化物向炔丙醇的直接SN2'加成反应合成。然而，该方法之前的实例涉及苛刻的反应条件，且中心手性向轴手性的转移不完全。在此我们表明，Cp2Zr(H)Cl能与炔丙醇的锌或镁醇盐反应，以良好的产率和高光学纯度生成丙二烯。通过该方法可获得二烷基、烷基芳基和二芳基丙二烯。此外，该反应能提供硅基取代的丙二烯、三取代丙二烯和末端丙二烯。
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