Intermolecular Redox-Neutral Carboamination of C–C Multiple Bonds Initiated by Transition-Metal-Catalyzed C–H Activation

Abstract

Carboamination of readily available feedstock-like alkenes, alkynes, and allenes has proven to be an efficient and powerful tool for the synthesis of diverse and valuable amine derivatives of relevance to medicinal chemistry, biochemistry, and material science. Among these developed carboamination methodologies, the direct use of the C–H activation strategy to leverage the carboamination process is particularly attractive due to the ubiquity of such bonds in organic molecules. In this review, we provide an overview of the development of intermolecular carboamination across C–C π-bonds initiated by C–H activation in a redox-neutral and nonannulative manner, with an emphasis on synthetic and mechanistic aspects. In principle, this review summarized these reactions with a key feature of involving an initial C–H metalation followed by an intermolecular migratory insertion into π-bonds and terminated by an electrophilic amination quenching, and thus, it is ordered by the sources of C- and N-based functionalities and further divided by π-compounds.

Catalytic Radical‐Polar Crossover Non‐Classical Semipinacol Rearrangements: The Sustainable Approach

“…The recent generation is seeing electrocatalysis as one of the abundant and effective solutions to the transition metal catalysis in various chemical transformations and not surprisingly, this particular technique has come forward as a potential replacement for the acid/metalcatalysed/promoted semipinacol rearrangement. [49][50][51][52][53][54][55] Although it sounds like a new method, the first example of such kind along with the feasibility study was documented by Corey and co-workers back in 1960. They could successfully employ the anodic oxidation of α-hydroxy carboxylic acids 28 a-c i. e. the Kolbe's electrolysis for the synthesis of various ketones 28 d-f.…”

Ir(iii)/Ag(i)-catalyzed directly C–H amidation of arenes with OH-free hydroxyamides as amidating agents

“…Transition-metal-catalyzed C–H functionalization has become powerful tools for synthesis of non-cyclic or cyclic artificial molecule, which complementary to traditional synthesis methods. 9 C–H functionalization reaction has unparalleled advantages in the construction of chemical bonds and compounds. 10 Particularly, significant progress has been made in C–H bond amidation reactions in recent years.…”

The Effect of Basic Ligands and Alkenes on the Regioselectivity of C−H Additions of Tertiary Amines to Alkenes

“…[2À 4] Among the established approaches, transition metal catalyzed direct CÀ H addition reaction of aniline derivatives to olefins have been emerging as one of the most powerful and atom-economical strategies. [3] In particular, rareearth organometallic complexes have been successfully utilized as competent and unique catalysts for the regioselective CÀ H functionalization of tertiary anilines with unactivated olefins by the groups of Hou and Xu. [5] Arising from the high affinity toward heteroatoms, strong basicity of rare-earth metal alkyl complexes as well as high reactivity towards C=C bond, distinct activity and selectivity were obtained in the rare-earth metal mediated processes.…”