摘要/Abstract
烯丙位手性中心不仅广泛存在于天然产物和药物活性分子中, 也是有机合成中的重要合成砌块. 过渡金属催化烯基金属试剂作为亲核试剂的不对称加成或偶联反应是构建这一结构非常有吸引力的策略之一. 在众多金属催化剂中, 铁钴镍铜等丰产金属由于其独特的催化活性以及低毒性、环境友好等优点而被用来代替铑钯等稀有金属应用于此类不对称烯基化反应中, 并取得了显著的成果. 基于此, 本文将综述丰产金属催化的烯基金属试剂参与的不对称烯基化反应研究进展. 主要包括: (1)钴催化的不对称烯基化反应, (2)镍催化的不对称烯基化反应, (3)铜催化的不对称烯基化反应以及(4)其他丰产金属催化的不对称烯基化反应等四部分.
关键词: 丰产金属催化, 烯基金属试剂, 不对称烯基化, 不对称加成, 不对称偶联
Allylic chiral centers are widely present in natural products and pharmaceutically active molecules, and play a vital role in the construction of organic compounds through pericyclic reactions, oxidations or reductions and other transformations. The transition metal-catalyzed asymmetric addition or coupling reaction using alkenyl metal nucleophiles is one of the most attractive strategies for the synthesis of these structures. Among the many metal catalysts, earth-abundant transition metals such as iron, cobalt, nickel and copper have been used to replace precious metals such as rhodium and palladium, and have gained attention for use in enantioselective alkenylations. Indeed, remarkable advances have been achieved with these catalysts due to their unique catalytic activity, low toxicity and environmentally friendliness. The earth-abundant transition metals are known to undergo facile one electron oxidation state changes. In the reaction process, the earth-abundant transition metals have the ability to undergo two-electron transfer and single-electron transfer processes, therefore they have more valence changes and catalytic pathways which can be exploited. Based on this, this article will review the latest research in earth-abundant metal-catalyzed enantioselective alkenylation using alkenyl metal reagents. It is divided into four sections consisting of cobalt-catalyzed enantioselective alkenylations using alkenyl metal reagents, nickel-catalyzed enantioselective alkenylations using alkenyl metal reagents, copper-catalyzed enantioselective alkenylations using alkenyl metal reagents, and other earth-abundant transition metals catalyzed enantioselective alkenylations using alkenyl metal reagents.
Key words: earth-abundant metal catalysis, alkenyl metal reagent, enantioselective alkenylation, asymmetric addition, asymmetric coupling
PDF全文下载地址:
点我下载PDF
