镍催化未活化烯烃的不对称还原芳基-烯丙基化反应。
Nickel-catalyzed asymmetric reductive aryl-allylation of unactivated alkenes.
作者信息
Lin Zhiyang, Jin Youxiang, Hu Weitao, Wang Chuan
机构信息
Hefei National Laboratory for Physical Science at the Microscale, Department of Chemistry, Center for Excellence in Molecular Synthesis, University of Science and Technology of China 96 Jinzhai Road Hefei Anhui 20237 P. R. China
出版信息
Chem Sci. 2021 Apr 9;12(19):6712-6718. doi: 10.1039/d1sc01115d.
Herein we report a nickel-catalyzed asymmetric reductive aryl-allylation of aryl iodide-tethered unactivated alkenes, wherein both acyclic allyl carbonates and cyclic vinyl ethylene carbonates can serve as the coupling partners. Furthermore, the direct use of allylic alcohols as the electrophilic allyl source in this reaction is also viable in the presence of BOC anhydride. Remarkably, this reaction proceeds with high linear/branched-, /- and enantio-selectivity, allowing the synthesis of various chiral indanes and dihydrobenzofurans (50 examples) containing a homoallyl-substituted quaternary stereocenter with high optical purity (90-98% ). In this reductive reaction, the use of pregenerated organometallics can be circumvented, giving this process good functionality tolerance and high step-economy.
在此，我们报道了一种镍催化的、芳基碘连接的未活化烯烃的不对称还原芳基-烯丙基化反应，其中无环碳酸烯丙酯和环状碳酸乙烯基亚乙酯均可作为偶联试剂。此外，在酸酐存在下，直接使用烯丙醇作为该反应中的亲电烯丙基源也是可行的。值得注意的是，该反应具有高的线性/支化选择性、E/Z选择性和对映选择性，能够合成各种含有高光学纯度（90-98%）的高烯丙基取代季碳立体中心的手性茚满和二氢苯并呋喃（50个实例）。在该还原反应中，可以避免使用预生成的有机金属化合物，使得该过程具有良好的官能团耐受性和高步骤经济性。
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