Nitrile as a Versatile Directing Group for C(sp2)-H Functionalizations

作者:Ping, Yuanyuan; Wang, Liping; Ding, Qiuping*; Peng, Yiyuan
来源:Advanced Synthesis & Catalysis, 2017, 359(19): 3274-3291.
DOI:10.1002/adsc.201700684

摘要

The one-step direct regioselective functionaliztion of inert C(sp(2))-H bonds is an efficient and sustainable methodology for the synthesis of a variety of useful natural products and pharmaceutical intermediates. A range of functional groups have been widely used as directing group for various regioselective transformations. Among these, the weakly coordinating nitrile group has attracted much attention because it is a transformable, easily installed and readily removed directing group, which can be easily converted into a number of different functional groups, such as carboxyl, carbamoyl, aminomethyl, carbonyl, and heterocyclic functionalities. This review describes recent advances in nitrile-directed C-H functionalizations catalyzed by palladium(II), ruthenium(II), rhodium(III) and iridium(I) catalysts. The review is divided into sections related to ortho-, meta-, and para-C-H bond functionalizations, which are subdivided according to reaction type (olefination, arylation, halogenation, hydroxylation and acetoxylation). @@@ 1 Introduction @@@ 2 Nitrile-Directed ortho C-H Bond Functionalization @@@ 2.1 Nitrile-Directed ortho C-H Bond Arylation @@@ 2.2 Nitrile-Directed ortho C-H Bond Halogenation @@@ 2.3 Nitrile-Directed ortho-C-H Bond Olefination @@@ 2.4 Nitrile-Directed ortho-C-H Bond Alkoxylation @@@ 2.5 Nitrile-Directed ortho-C-H Bond Borylation @@@ 3 Nitrile-Directed meta-C-H Bond Functionalization @@@ 3.1 Nitrile-Directed meta-C-H Bond Olefination @@@ 3.2 Nitrile-Directed meta C-H Bond Arylation @@@ 3.3 Nitrile-Directed meta C-H Bond Hydroxylation and Acetoxylation @@@ 4 Nitrile-Directed para-C-H Bond Functionalization @@@ 5 Conclusion