Described herein is the development of an arenophile-mediated, nickel-catalyzed dearomative trans-1,2-carboamination protocol. A range of readily available aromatic compounds was converted to the corresponding dienes using Grignard reagents as nucleophiles. This strategy provided products with exclusive trans-selectivity and high enantioselectivity was observed in case of benzene and naphthalene. The utility of this methodology was showcased by controlled and stereoselective preparation of small, functionalized molecules.
A concise synthesis of (+)-pancratistatin and (+)-7-deoxypancratistatin from benzene using an enantioselective, dearomative carboamination strategy has been achieved. This approach, in combination with the judicious choice of subsequent olefin-type difunctionalization reactions, permits rapid and controlled access to a hexasubstituted core. Finally, minimal use of intermediary steps as well as direct, late stage C-7 hydroxylation provides both natural products in six and seven operations.
本文介绍了一种由亲腈剂介导、
镍催化的脱芳香反式-1,2-羧化反应。以
格氏试剂为亲核剂,一系列现成的芳香族化合物被转化为相应的二烯。这种方法提供的产品具有独特的反式选择性,苯和
萘的对映选择性也很高。通过控制和立体选择性制备功能化小分子,展示了这一方法的实用性。
利用对映选择性脱芳羧化策略,以苯为原料简便地合成了 (+)-pancratistatin 和 (+)-7-deoxypancratistatin 。这种方法与后续烯烃类双官能化反应的明智选择相结合,可以快速、可控地获得六代核心。最后,使用最少的中间步骤以及直接的后期 C-7 羟基化反应,只需六次和七次操作就能得到两种天然产品。