氨基甲酸酯广泛存在于天然产物、药物和农药分子中，同时也是一种常见的C—H键活化导向官能团。在过渡金属催化下，氨基甲酸酯可导向底物分子氨基邻位的C—H键活化，经六元环金属中间体，再与其他偶联试剂偶联实现新的官能团化。本文系统总结了其在C—H键活化反应中的应用，具体包括：（1）N-芳基氨基甲酸酯、氨基甲酸芳酯和氨基甲酸烯醇酯可在过渡金属Pd、Rh、Ru和Ir等催化下发生芳基邻位sp2 C—H键活化与官能团化反应，得到卤化、芳基化、环化和烯基化产物；（2）氨基甲酸烯醇酯可在Rh催化下发生烯基β-位sp2 C—H键活化与官能团化反应，得到烯基化和烯丙基化产物；（3）氨基邻位具有活性氢的N-烷基氨基甲酸酯可在Pd、Cu、Fe甚至无过渡金属催化下发生sp3 C—H键活化与官能团化反应，得到酰氧化、烷基化和芳基化产物。在芳香sp2 C—H键活化中，取代基的电子效应和空间位阻效应均对产物产率和选择性有重要影响。大多数情况下，给电子与空间位阻较小的取代基有利于反应的顺利进行。此外，当底物为N-烷氧羰基保护的苄胺、四氢异喹啉或1，2-二氢喹啉时，因氨基邻位独特的高活性，可在Cu、Fe甚至无金属催化剂或光催化下催化氨基邻位sp3 C—H键活化反应，还可以实现不对称诱导，获得非常高的对映选择性。希望本文总结的内容能促进氨基甲酸酯在C—H键活化反应中的进一步应用。
Carbamates widely exist in natural products, drugs and pesticides, and have also been utilized as directing groups in the C-H bond activation. Generally, in the presence of transition metals, the carbamate group can selectively direct the ortho C-H bond activation of substrates to realize the coupling approaches with various coupling reagents through metal-bearing six-membered ring intermediates. The application of carbamates in the C-H bond activation reactions has been systematically summarized, including:(1) sp2 C-H bond activation and functionalization of N-aryl carbamates, and aryl carbamates under the catalysis of Pd, Rh, Ru, or Ir to afford the corresponding halogenation, arylation, cyclization, and alkenylation products;(2) sp2 C-H bond activation and functionalization of alkenyl carbamates in the presence of Rh to afford the corresponding alkenylation and allylation products;(3) sp3 C-H bond activation and functionalization of N-dialkyl carbamates in the presence of Pd, Cu, Fe or even the transition-metal-free conditions to afford the acetoxylation, alkylation or arylation products. During the aromatic sp2 C-H bond activation approaches, both electronic and steric effects control the reaction yields and regioselectivities. In most cases, substrates bearing electron donating and less steric hindrance groups show better reactivity. Moreover, owing to the high activity of vicinal position of amines, the C-H functionalization of benzylamine, tetrahydroisoquinolines or 1,2-dihydroquinoline, bearing N-alkoxycarbonyl, can be carried out under the catalysis of copper, iron, or even the transition-metal-free conditions, some of which can also show high enantioselectivity through the asymmetric induction. The review can provide some guidance to promote the further development and application of carbamates in C-H bond activation reactions.
Contents
1 Introduction
2 Ortho-directed sp2 C-H bond activation reactions of N-aryl carbamates
2.1 Pd-catalyzed reactions
2.2 Rh-catalyzed reactions
2.3 Ru-catalyzed reactions
2.4 Ir-catalyzed reactions
3 Ortho-directed sp2 C-H bond activation reactions of aryl carbamates
3.1 Pd-catalyzed reactions
3.2 Rh-catalyzed reactions
3.3 Ru-catalyzed reactions
3.4 Ir-catalyzed reactions
4 Ortho-directed sp2 C-H bond activation reactions of N-alkenyl carbamates and alkenyl carbamates
5 Directing sp3 C-H bond activation reactions of N-dialkyl carbamates
6 Non-directing sp3 C-H bond activation reactions of N-dialkyl carbamates
7 Conclusion
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