通过锆介导的烯丙基氯的S(N)2'取代反应实现受保护烯丙醇的区域和立体特异性形成。
Regio- and stereospecific formation of protected allylic alcohols via zirconium-mediated S(N)2' substitution of allylic chlorides.
作者信息
Fox Richard J, Lalic Gojko, Bergman Robert G
机构信息
Department of Chemistry, University of California, Berkeley, California 94720, USA.
出版信息
J Am Chem Soc. 2007 Nov 21;129(46):14144-5. doi: 10.1021/ja075967i. Epub 2007 Oct 31.
Abstract
A new, highly regio- and stereospecific S2' substitution reaction between a zirconium oxo complex and allylic chloride has been achieved. The resulting allylic alcohol or TBS-protected allylic ether products were isolated in good to excellent yields with a wide range of -allylic chlorides. A mechanism for the S2' allylic substitution consistent with kinetic, stereochemical and secondary isotope effect studies was proposed.
摘要
实现了一种新型的、具有高度区域和立体特异性的氧代锆配合物与烯丙基氯之间的S2'取代反应。使用多种烯丙基氯，以良好至优异的产率分离得到了相应的烯丙醇或TBS保护的烯丙基醚产物。提出了一种与动力学、立体化学和二级同位素效应研究相一致的S2'烯丙基取代反应机理。
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