使用二硼甲烷试剂的催化SN2'-和对映选择性烯丙基取代及其在合成中的应用。
Catalytic SN2'- and Enantioselective Allylic Substitution with a Diborylmethane Reagent and Application in Synthesis.
作者信息
Shi Ying, Hoveyda Amir H
机构信息
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA, 02467, USA.
出版信息
Angew Chem Int Ed Engl. 2016 Mar 1;55(10):3455-8. doi: 10.1002/anie.201600309. Epub 2016 Feb 4.
Abstract
A catalytic method for the site- and enantioselective addition of commercially available di-B(pin)-methane to allylic phosphates is introduced (pin=pinacolato). Transformations may be facilitated by an NHC-Cu complex (NHC=N-heterocyclic carbene) and products obtained in 63-95 % yield, 88:12 to >98:2 S(N)2'/S(N)2 selectivity, and 85:15-99:1 enantiomeric ratio. The utility of the approach, entailing the involvement of different catalytic cross-coupling processes, is highlighted by its application to the formal synthesis of the cytotoxic natural product rhopaloic acid A.
摘要
介绍了一种将市售的二硼酸频哪醇酯甲烷对烯丙基磷酸酯进行位点和对映选择性加成的催化方法（pin = 频哪醇硼酸酯）。NHC-Cu配合物（NHC = N-杂环卡宾）可促进反应转化，产物收率为63-95%，S(N)2'/S(N)2选择性为88:12至>98:2，对映体比例为85:15 - 99:1。该方法涉及不同的催化交叉偶联过程，通过将其应用于细胞毒性天然产物罗帕洛酸A的形式合成，突出了其效用。
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