Phosphorus-Containing Groups Assisted Transition Metal Catalyzed C-H Activation Reactions

Abstract

Over the last few decades, transition metal-catalyzed direct C-H activation with the assistance of a coordinating directing group has emerged as an atom- and stepeconomical synthetic tools to transform C–H bonds into carbon-carbon or carbonheteroatom bonds. Although the strategies involving regioselective C–H cleavage assisted by various directing groups have been extensively reviewed in the literature, we now attempt to give an overview of the recent advances on phosphorus-containing functional group assisted C-H activation reactions catalyzed by transition-metal catalysts including mechanistic study and synthetic applications. The discussion is directed towards C-H olefination, C-H activation/cyclization, C-H arylation, C-H amination, C-H hydroxylation and acetoxylation as well as miscellaneous C-H activation.

Recent Advances in Alkenyl sp2 C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

“…Enol phosphates often serve as a versatile alternative to the corresponding halides and triflates to engage in the transition-metal-catalyzed coupling reactions because of their high stability and ready availability. Despite the remarkable achievements in phosphorus-containing groups assisted C−H activation reactions, 664 the direct alkenyl C(sp 2 )−H functionalization of enol phosphates is extremely difficult to achieve. To address this issue, Loh and co-workers expanded their olefinic C−H functionalization strategy and reported in 2015 the unprecedented example of Cp*Rh(III)catalyzed coupling reactions of enol phosphates with a broad array of activated alkenes, alkynes as well as allenes, leading to the synthesis of a series of synthetically valuable alkenylated and hydroalkenylated enol phosphates with good regio-and stereoselectivity (Scheme 409).…”

Phosphorus‐Directed C−H Borylation

“…Examples of methods that could afford late‐stage functionalization of organophosphorus moieties through C−H functionalization began to be introduced in 2011 [80–88] . These transformations have been detailed in two recent reviews [89–90] and highlight the pioneering work by Kuninobu and Takai, [91] Satoh and Miura, [92–95] Glorius, [96] Kim and Lee, [97–105] Moon, [106] Yang, [107–109] and Park and Chang [110–111] . Among these valuable transformations are examples of C−H alkylation, alkenylation, arylation, amination, oxygenation, and cyanation.…”