Looking deep into C–H functionalization: the synthesis and application of cyclopentadienyl and related metal catalysts

Abstract

Metal catalyzed C–H functionalization offers a versatile platform for methodology development and a wide variety of reactions now exist for the chemo- and site-selective functionalization of organic molecules. Cyclopentadienyl-metal (CpM)...

Designed Iron Catalysts for Allylic C−H Functionalization of Propylene and Simple Olefins

“…As an initial hypothesis, we posited that increasing the π‐acidity of the cationic iron complex would improve catalyst efficiency by facilitating the deprotonation of the iron‐alkene complex. Bearing fewer electron‐donating alkyl substituents than Cp* and being readily prepared and modifiable, 2‐phenyltetrahydroindenyl (Cp W1 ) was considered as a ligand, and Fp W1 (thf)BF 4 was prepared and evaluated as a catalyst (henceforth, Fp X (thf)BF 4 represents [Fp X (thf)] + BF 4 − ) (Scheme 3b) [1a, 20] . To our delight, this novel catalyst led to higher yield than Fp*(thf)BF 4 .…”

Recent advances in metal directed C–H amidation/amination using sulfonyl azides and phosphoryl azides

“…C-H functionalization refers to a chemical process that involves the conversion of a C-H bond into another element or functional group (often represented as a functional group R), irrespective of the underlying mechanism. 37,38 This transformation can result in the introduction of various substituents such as halides, oxygen-, nitrogen-, or carbon-linked groups. Examples of such reactions include electrophilic aromatic substitutions (SEAr), radical additions, deprotonations, or C-H functionalizations catalyzed by transition metals.…”

“…Therefore, C-H acti-vation reactions can be considered a specific subset within the broader category of C-H functionalization reactions. A multitude of articles [37][38][39][40][41][42][43][44] have delved deeply into the complex inner workings and the myriad ways in which this reaction can manifest. In some recent forward-looking pieces by T. Dalton and his team 42 in 2021, and E. Weis 41 in 2022, a fascinating array of research areas were explored, all with the common goal of addressing the sustainability hurdles linked to the activation of C-H bonds.…”

Rh(i)-catalyzed site-selective hydroacylation of alkenyl-bearing allylic alcohols with non-chelating aldehydes controlled by in situ generated carbonyl group

“…In the past few decades, significant efforts have been put into developing highly regioselective and completely atom-economical hydroacylation of unsaturated hydrocarbons by transition metal catalysis, including Co, Ni, Ru, and Rh complexes. 1 Compared with intramolecular hydroacylation, intermolecular counterparts still face more practical challenges, such as reductive decarbonylation that ultimately results in catalyst deactivation. 2 In order to favor the desired reactivity over decarbonylation, the presence of a chelating group is a prerequisite for the successful implementation of the intermolecular hydroacylation reactions.…”