Conventional methods for carrying out carbon–hydrogen functionalization and carbon–nitrogen bond formation are typically conducted at elevated temperatures, and rely on expensive catalysts as well as the use of stoichiometric, and perhaps toxic, oxidants. In this regard, electrochemical synthesis has recently been recognized as a sustainable and scalable strategy for the construction of challenging carbon–carbon and carbon–heteroatom bonds. Here, electrosynthesis has proven to be an environmentally benign, highly effective and versatile platform for achieving a wide range of nonclassical bond disconnections via generation of radical intermediates under mild reaction conditions. This review provides an overview on the use of anodic electrochemical methods for expediting the development of carbon–hydrogen functionalization and carbon–nitrogen bond formation strategies. Emphasis is placed on methodology development and mechanistic insight and aims to provide inspiration for future synthetic applications in the field of electrosynthesis.

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Electrochemical strategies for C-H functionalization and C-N bond formation.

Borrowing hydrogen (or hydrogen autotransfer) reactions represent straightforward and sustainable C-N bond-forming processes. In general, precious metal-based catalysts are employed for this effective transformation. In recent years, the use of earth abundant and cheap non-noble metal catalysts for this process attracted considerable attention in the scientific community. Here we show that the selective N-alkylation of amines with alcohols can be catalysed by defined PNP manganese pincer complexes. A variety of substituted anilines are monoalkylated with different (hetero)aromatic and aliphatic alcohols even in the presence of other sensitive reducible functional groups. As a special highlight, we report the chemoselective monomethylation of primary amines using methanol under mild conditions.

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Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes.

Over the past few years, CuH-catalyzed hydroamination has been discovered and developed as a robust and conceptually novel approach for the synthesis of enantioenriched secondary and tertiary amines. The success in this area of research was made possible through the large body of precedent in copper(I) hydride catalysis and the well-explored use of hydroxylamine esters as electrophilic amine sources in related copper-catalyzed processes. This Minireview details the background, advances, and mechanistic investigations in CuH-catalyzed hydroamination.

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Copper Hydride Catalyzed Hydroamination of Alkenes and Alkynes

Transition-metal catalyzed reactions that are able to construct complex aliphatic amines from simple, readily available feedstocks have become a cornerstone of modern synthetic organic chemistry. I...

New Strategies for the Transition-Metal Catalyzed Synthesis of Aliphatic Amines.

Homogeneous catalysis of organic transformations by metal complexes has been mostly based on complexes of noble metals. In recent years, tremendous progress has been made in the field of base-metal catalysis, mostly with pincer-type complexes, such as iron, cobalt, nickel, and manganese pincer systems. Particularly impressive is the explosive growth in the catalysis by Mn-based pincer complexes, the first such complexes being reported as recently as 2016. This review covers recent progress in the field of homogeneously catalyzed reactions using pincer-type complexes of cobalt and manganese. Various reactions are described, including acceptorless dehydrogenation, hydrogenation, dehydrogenative coupling, hydrogen borrowing, hydrogen transfer, H–X additions, C–C coupling, alkene polymerization and N2 fixation, including their scope and brief mechanistic comments.

Homogeneous Catalysis by Cobalt and Manganese Pincer Complexes

Unusually-Coordinated Phosphorus Compounds. Part 39. Phosphatriafulvenes - Phosphaalkenes with Inverse Electron Density.

Unusually Coordinated Phosphorus Compounds. Part 24. Methylidynephosphane (HCP), a Novel Partner for 1,3-Dipolar Cycloaddition Reactions.

Peterson olefination of the sterically hindered cyclopropenones 1 with the lithium phosphides 2 yields the so far unknown phophatriafulvenes 3 and 4, which possess inverse electron densities. They are characterized by transition metal complex formation (--> 7, 8). Acylation of 3a with the carboxylic acid chlorides 11 leads to a great variety of P-acylphosphatriafulvenes 13a-s. They partly dimerize under formation of the 1,3-diphosphacyclobutanes 13 reversible 14.

Organophosphorus compounds .51. phosphatriafulvenes - phosphaalkenes with inverse electron-density

Phosphorus Compounds. Part 97. Synthesis of Polycyclic Phosphorus Cage Compounds Containing Diphosphirane and Phosphirane Units by Tandem Diels‐Alder and Ene Reactions: A Contribution to the Cycloaddition and Enophile Chemistry of Phosphaalkynes.

H. Heydt

Papers

Unusually-Coordinated Phosphorus Compounds. Part 39. Phosphatriafulvenes - Phosphaalkenes with Inverse Electron Density.

Unusually Coordinated Phosphorus Compounds. Part 24. Methylidynephosphane (HCP), a Novel Partner for 1,3-Dipolar Cycloaddition Reactions.

Organophosphorus compounds .51. phosphatriafulvenes - phosphaalkenes with inverse electron-density

Phosphorus Compounds. Part 97. Synthesis of Polycyclic Phosphorus Cage Compounds Containing Diphosphirane and Phosphirane Units by Tandem Diels‐Alder and Ene Reactions: A Contribution to the Cycloaddition and Enophile Chemistry of Phosphaalkynes.

Phosphorus Compounds with Unusual Coordination. Part 13. Trapping Reactions of Phenyl Thioxophosphane by [4 + 1| Cycloaddition with o-Quinones.