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机构地区:[1]北京大学天然药物及仿生药物国家重点实验室,北京100191
出 处:《化学学报》2015年第12期1231-1234,共4页Acta Chimica Sinica
基 金:国家重点基础研究发展计划(973计划;No.2015CB856600);国家自然科学基金(Nos.21325206;21172006);青年拔尖人才支持计划;国家教育部博士点基金(No.20120001110013)资助~~
摘 要:近些年来,基于导向策略的Pd催化间位C(sp^2)—H键活化反应取得了重要进展.人们通过远程导向策略,针对不同底物发展了多种U型导向基,在一些单保护氨基酸配体(MPAA)的协助下,实现了多种底物的烯基化、芳基化和乙酰氧基化反应.最近,人们又将Pd催化导向邻位C—H键活化和Catellani反应相结合,使用结构简单的导向基实现了高选择性的间位C—H键的烷基化和芳基化反应.这两种策略均可用于一些生物活性分子或者药物分子前体的后期修饰与合成当中.本文将针对这一领域的最新研究进展做一概述.In recent years, remarkable progress has been achieved in Pd-catalyzed meta-C(sp^2)—H bond activation with directing groups. Based on remote activation strategy, a series of U-shaped directing groups have been devised by Yu and others and have been utilized in the olefination, arylation and acetoxylation of different types of substrates with the assistance of mono-protected amino acids(MPAA). Very recently, Yu reported the Pd-catalyzed meta-C(sp^2)—H bond activation via the tandem reaction of ortho-C(sp^2)—H bond activation and Catellani reaction using simple directing groups, in which alkylation and arylation could all be realized under the Pd/norbornene catalytic system. Dong and co-workers developed arylation of the meta-C(sp^2)—H bond of N,N-dimethylbenzylamine with similar strategy. It is noteworthy that these above mentioned meta-C(sp^2)—H bond activation protocols could be applied in the late-stage modification and the synthesis of some biologically active molecules and pharmaceutical intermediates. This manuscript will highlight the latest advances in Pd-catalyzed meta-C(sp^2)—H bond activation with directing groups.
关 键 词:钯 间位C—H键活化 远程导向 Catellani反应 降冰片烯
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