Enantio- and Diastereoselective Suzuki-Miyaura Coupling with Racemic Bicycles
Enantio- and Diastereoselective Suzuki-Miyaura Coupling with Racemic Bicycles
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对映体和非对映选择性 Suzuki-Miyaura 与外消旋自行车的偶联
DOI：
10.1002/ange.201906478
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发表时间：
2019
影响因子：
--
通讯作者：
Goetzke F
中科院分区：
文献类型：
--
作者：
Goetzke F
本文中，我们描述了铑催化的外消旋稠合双环烯丙基氯化物和硼酸之间的对映体和非对映体选择性Suzuki-Miyaura交叉偶联。高度立体选择性的转化允许芳基、杂芳基和烯基硼酸的偶联，并获得官能化的双环环戊烯，其可以转化为具有多达五个连续立体中心的其他五元环骨架。初步的机理研究表明，这些反应的发生与相对立体化学的整体保留，并且对于假对称烯丙基氯起始材料是对映收敛的。此外，不具有伪对称性的双环烯丙基氯起始材料经历高度对映选择性区域发散反应。
Herein, we describe a rhodium‐catalyzed enantio‐ and diastereoselective Suzuki–Miyaura cross‐coupling between racemic fused bicyclic allylic chlorides and boronic acids. The highly stereoselective transformation allows for the coupling of aryl, heteroaryl, and alkenyl boronic acids and gives access to functionalized bicyclic cyclopentenes, which can be converted into other five‐membered‐ring scaffolds with up to five contiguous stereocenters. Preliminary mechanistic studies suggest that these reactions occur with overall retention of the relative stereochemistry and are enantioconvergent for pseudo‐symmetric allylic chloride starting materials. In addition, a bicyclic allylic chloride starting material without pseudo‐symmetry undergoes a highly enantioselective regiodivergent reaction.