Research and industrial interest in radical C–H activation/radical cross-coupling chemistry has continuously grown over the past few decades. These reactions offer fascinating and unconventional approaches toward connecting molecular fragments with high atom- and step-economy that are often complementary to traditional methods. Success in this area of research was made possible through the development of photocatalysis and first-row transition metal catalysis along with the use of peroxides as radical initiators. This Review provides a brief and concise overview of the current status and latest methodologies using radicals or radical cations as key intermediates produced via radical C–H activation. This Review includes radical addition, radical cascade cyclization, radical/radical cross-coupling, coupling of radicals with M–R groups, and coupling of radical cations with nucleophiles (Nu).

Recent Advances in Radical C-H Activation/Radical Cross-Coupling.

The area of catalysis of radical reactions has recently flourished. Various reaction conditions have been discovered and explained in terms of catalytic cycles. These cycles rarely stand alone as unique paths from substrates to products. Instead, most radical reactions have innate chains which form products without any catalyst. How do we know if a species added in "catalytic amounts" is a catalyst, an initiator, or something else? Herein we critically address both catalyst-free and catalytic radical reactions through the lens of radical chemistry. Basic principles of kinetics and thermodynamics are used to address problems of initiation, propagation, and inhibition of radical chains. The catalysis of radical reactions differs from other areas of catalysis. Whereas efficient innate chain reactions are difficult to catalyze because individual steps are fast, both inefficient chain processes and non-chain processes afford diverse opportunities for catalysis, as illustrated with selected examples.

Catalysis of Radical Reactions: A Radical Chemistry Perspective.

Oxidative Coupling between Two Hydrocarbons: An Update of Recent C–H Functionalizations

/pdf/chemicals-from-alkynes-with-palladium-catalysts-2z3b447mxh.pdf

Chemicals from Alkynes with Palladium Catalysts

Transition metal-catalyzed C–H bond functionalizations have been the focus of intensive research over the last decades for the formation of C–C bonds from unfunctionalized arenes, heteroarenes, alkenes These direct transformations provide new approaches in synthesis with high atom- and step-economy compared to the traditional catalytic cross-coupling reactions However, such methods still suffer from several limitations including functional group tolerance and the lack of regioselectivity In addition, they often require harsh reaction conditions and some of them need the use of strong oxidant, in a stoichiometric amount, avoiding these processes to be truly eco-friendly The use of photoredox catalysis has contributed to a significant expansion of the scope of C(sp2)–H bond functionalizations which include the direct arylations, (perfluoro)alkylations, acylations, and even cyanations Most of these transformations involve the photochemical induced generation of a radical followed by its regioselective a

Photoredox Catalysis for Building C-C Bonds from C(sp2)-H Bonds.

Silver-catalyzed synthesis of 3-phosphorated coumarins via radical cyclization of alkynoates and dialkyl H-phosphonates.

Regioselective Palladium-Catalyzed Phosphonation of Coumarins with Dialkyl H-Phosphonates via C–H Functionalization

Silver-catalyzed carbonphosphonation of α,α-diaryl allylic alcohols is achieved. A series of γ-ketophosphonates with different substituents were readily obtained. The mechanistic study indicated that the reaction was initiated by the addition of P-radicals, which sequentially undergo 1,2-migration of an aryl group to form C(Ar)–C(sp3) bonds.

Silver-catalyzed carbonphosphonation of α,α-diaryl allylic alcohols: synthesis of β-aryl-γ-ketophosphonates

Copper-catalyzed cross-dehydrogenative-coulping (CDC) of coumarins with cyclic ethers and cycloalkane

A new palladium(II) complex based on N,N-dimethylethanolamine, (SP-4-1′)-bis[N,N-dimethylaminoethoxy-kN,O]palladium(II) which coordinates with two moles of AcOH, has been synthesized. The structure of the complex has been established by X-ray diffraction analysis. Using this complex as a catalyst, a series of conjugated enynes were successfully synthesized by Sonogashira cross-coupling reaction in the absence of co-catalyst CuX and any ligand at room temperature during 20 hours affording the corresponding products in moderate to excellent yields. The optimized catalytic systems are tolerant in the presence of a broad variety of functional groups in the substrates. The catalytic system was found to be ineffective for vinyl chloride. Moreover, it was found that (Z)-β-bromostyrene reacts with terminal alkynes with retention of the steric configuration and the transformation of most of the Z-isomer did not occur in this reaction.

Discovery of A Novel Palladium Catalyst for the Preparation of Enynes with a Copper- and Ligand-Free Sonogashira Reaction

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