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      Phosphorylation of arenes, heteroarenes, alkenes, carbonyls and imines by dehydrogenative cross-coupling of P(O)–H and P(R)–H

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          Abstract

          This review offers an ample opportunity to take a journey through recent advancements in C–P bond formation reactions, along with their mechanistic pathways.

          Abstract

          Organophosphorous compounds have recently emerged as a powerful class of compounds with widespread applications, such as in bioactive natural products, pharmaceuticals, agrochemicals and organic materials, and as ligands in catalysis. The preparation of these compounds requires synthetic techniques with novel catalytic systems varying from transition metal, photo- and electrochemical catalysis to transformations without metal catalysts. Over the past few decades, the addition of P–H bonds to alkenes, alkynes, arenes, heteroarenes and other unsaturated substrates in hydrophosphination and other related reactions via the above-mentioned catalytic processes has emerged as an atom economical approach to obtain organophosphorus compounds. In most of the catalytic cycles, the P–H bond is cleaved to yield a phosphorus-based radical, which adds onto the unsaturated substrate followed by reduction of the corresponding radical yielding the product.

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          Most cited references218

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          Catalytic dehydrogenative cross-coupling: forming carbon-carbon bonds by oxidizing two carbon-hydrogen bonds.

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            Merging photoredox catalysis with organocatalysis: the direct asymmetric alkylation of aldehydes.

            Photoredox catalysis and organocatalysis represent two powerful fields of molecule activation that have found widespread application in the areas of inorganic and organic chemistry, respectively. We merged these two catalysis fields to solve problems in asymmetric chemical synthesis. Specifically, the enantioselective intermolecular alpha-alkylation of aldehydes has been accomplished using an interwoven activation pathway that combines both the photoredox catalyst Ru(bpy)3Cl2 (where bpy is 2,2'-bipyridine) and an imidazolidinone organocatalyst. This broadly applicable, yet previously elusive, alkylation reaction is now highly enantioselective and operationally trivial.
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              Cross-dehydrogenative coupling (CDC): exploring C-C bond formations beyond functional group transformations.

              Synthetic chemists aspire both to develop novel chemical reactions and to improve reaction conditions to maximize resource efficiency, energy efficiency, product selectivity, operational simplicity, and environmental health and safety. Carbon-carbon bond formation is a central part of many chemical syntheses, and innovations in these types of reactions will profoundly improve overall synthetic efficiency. This Account describes our work over the past several years to form carbon-carbon bonds directly from two different C-H bonds under oxidative conditions, cross-dehydrogenative coupling (CDC). We have focused most of our efforts on carbon-carbon bonds formed via the functionalization of sp(3) C-H bonds with other C-H bonds. In the presence of simple and cheap catalysts such as copper and iron salts and oxidants such as hydrogen peroxide, dioxygen, tert-butylhydroperoxide, and 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ), we can directly functionalize various sp(3) C-H bonds by other C-H bonds without requiring preactivation. We demonstrate (1) reaction of alpha-C-H bonds of nitrogen in amines, (2) reaction of alpha-C-H bonds of oxygen in ethers, (3) reaction of allylic and benzylic C-H bonds, and (4) reaction of alkane C-H bonds. These CDC reactions can tolerate a variety of functional groups, and some can occur under aqueous conditions. Depending on the specific transformation, we propose the in situ generation of different intermediates. These methods provide an alternative to the separate steps of prefunctionalization and defunctionalization that have traditionally been part of synthetic design. As a result, these methods will increase synthetic efficiencies at the most fundamental level. On an intellectual level, the development of C-C bond formations based on the reaction of only C-H bonds (possibly in water) challenges us to rethink some of the most fundamental concepts and theories regarding chemical reactivities. A successful reaction requires the conventionally and theoretically less reactive C-H bonds to react selectively in the presence of a variety of functional groups. With further investigation, we expect that C-C bond formations based on cross-dehydrogenative coupling will have a positive economic and ecological impact on the next generation of chemical syntheses.

                Author and article information

                Contributors
                (View ORCID Profile)
                Journal
                OBCRAK
                Organic & Biomolecular Chemistry
                Org. Biomol. Chem.
                Royal Society of Chemistry (RSC)
                1477-0520
                1477-0539
                January 19 2022
                2022
                : 20
                : 3
                : 498-537
                Affiliations
                [1 ]Department of Chemistry, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi-110016, India
                Article
                10.1039/D1OB02003J
                1bfac5bf-8233-4808-be04-3e86e03d0d66
                © 2022

                http://rsc.li/journals-terms-of-use

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