Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, United States.
J Am Chem Soc. 2013 May 8;135(18):6830-3. doi: 10.1021/ja402916z. Epub 2013 Apr 24.
A general, highly selective asymmetric redox-relay oxidative Heck reaction using achiral or racemic acyclic alkenols and boronic acid derivatives is reported. This reaction delivers remotely functionalized arylated carbonyl products from acyclic alkenol substrates, with excellent enantioselectivity under mild conditions, bearing a range of useful functionality. A preliminary mechanistic investigation suggests that the regioselectivity of the initial migratory insertion is highly dependent on the electronic nature of the boronic acid and more subtle electronic effects of the alkenyl alcohol.
本文报道了一种通用的、高选择性的不对称氧化还原接力型 Heck 反应,可用于手性或外消旋非环烯烃醇和硼酸衍生物。该反应在温和条件下,以优异的对映选择性,从非环烯烃醇底物中得到远程官能化的芳基化羰基产物,具有广泛的有用功能。初步的机理研究表明,初始迁移插入的区域选择性高度依赖于硼酸的电子性质以及烯丙醇更细微的电子效应。