Direct phosphorylation of benzylic C–H bonds under transition metal-free conditions forming sp<sup>3</sup>C–P bonds

Li, Qiang; Zhao, Chang‐Qiu; Chen, Tieqiao; Han, Li‐Biao

doi:10.1039/d2ra02812c

Cited by 3 publications

(1 citation statement)

References 102 publications

(27 reference statements)

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“…( Hirao et al, 1981 ; Petrakis and Nagabhushan, 1987 ; Gelman et al, 2003 ; Vaillard et al, 2007 ; Andaloussi et al, 2009 ; Luo and Wu, 2009 ; Berrino et al, 2010 ; Bruch et al, 2010 ; Zhuang et al, 2011 ; Zhao et al, 2012 ; Hu et al, 2013 ). Recently, new variants of C–H bond phosphorylation have been proposed, for example, transition metal catalysis ( Klein et al, 2007 ; Budnikova and Sinyashin, 2015 ; Budnikova et al, 2017 ; Shen et al, 2019 ; Liu et al, 2021b ; Guo et al, 2021 ; Ma et al, 2021 ; Zhao et al, 2021 ; Li et al, 2022a ; Li et al, 2022b ; Chen et al, 2022 ; Ji et al, 2022 ) or radical aromatic phosphorylation ( Gao et al, 2017 ; Gao et al, 2018 ; Cai et al, 2019 ; Mai et al, 2019 ; Chen et al, 2020 ; Liu et al, 2020 ; Rawat et al, 2020 ) (photoinitiated or catalyzed by the same metals or other activators), which provide a direct atom-economical road to C-P functionalized products of different nature (alkenes, alkanes, arenes).…”

Section: Introductionmentioning

confidence: 99%

Recent advances in electrochemical C—H phosphorylation

et al. 2022

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The activation of C–H bond, and its direct one-step functionalization, is one of the key synthetic methodologies that provides direct access to a variety of practically significant compounds. Particular attention is focused on modifications obtained at the final stages of the synthesis of complicated molecules, which requires high tolerance to the presence of existing functional groups. Phosphorus is an indispensable element of life, and phosphorus chemistry is now experiencing a renaissance due to new emerging applications in medicinal chemistry, materials chemistry (polymers, flame retardants, organic electronics, and photonics), agricultural chemistry (herbicides, insecticides), catalysis (ligands) and other important areas of science and technology. In this regard, the search for new, more selective, low-waste synthetic routes become relevant. In this context, electrosynthesis has proven to be an eco-efficient and convenient approach in many respects, where the reagents are replaced by electrodes, where the reactants are replaced by electrodes, and the applied potential the applied potential determines their “oxidizing or reducing ability”. An electrochemical approach to such processes is being developed rapidly and demonstrates some advantages over traditional classical methods of C-H phosphorylation. The main reasons for success are the exclusion of excess reagents from the reaction system: such as oxidants, reducing agents, and sometimes metal and/or other improvers, which challenge isolation, increase the wastes and reduce the yield due to frequent incompatibility with these functional groups. Ideal conditions include electron as a reactant (regulated by applied potential) and the by-products as hydrogen or hydrocarbon. The review summarizes and analyzes the achievements of electrochemical methods for the preparation of various phosphorus derivatives with carbon-phosphorus bonds, and collects data on the redox properties of the most commonly used phosphorus precursors. Electrochemically induced reactions both with and without catalyst metals, where competitive oxidation of precursors leads to either the activation of C-H bond or to the generation of phosphorus-centered radicals (radical cations) or metal high oxidation states will be examined. The review focuses on publications from the past 5 years.

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Section: Introductionmentioning

confidence: 99%

Recent advances in electrochemical C—H phosphorylation

et al. 2022

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C(sp3) P cross-coupling of alkyl substrates with P(O) H compounds and phosphites

Tang,

Ni,

Chen

2024

Tetrahedron Letters

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Ligand-Free Iron-Catalyzed Construction of C–P Bonds via Phosphorylation of Alcohols: Synthesis of Phosphine Oxides and Phosphine Compounds

Gan,

Ye,

et al. 2024

J. Org. Chem.

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An efficient method for the construction of C− P(V) and C−P(III) bonds via the iron-catalyzed phosphorylation of alcohols under ligand-free conditions is disclosed. This strategy represents a straightforward process to prepare a series of phosphine oxides and phosphine compounds in good to excellent yields from the readily available alcohols and P−H compounds. A plausible mechanism is also proposed. We anticipate that this mode of transforming simple alcohols would apply in chemical synthesis widely.

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Direct phosphorylation of benzylic C–H bonds under transition metal-free conditions forming sp³C–P bonds

Abstract: Direct phosphorylation of benzylic C–H bonds with secondary phosphine oxides was first realized. The reaction was performed in organo/aqueous biphasic system and under transition metal-free conditions, proceeding via the cross dehydrogenative coupling.

Cited by 3 publications

References 102 publications

Recent advances in electrochemical C—H phosphorylation

Recent advances in electrochemical C—H phosphorylation

C(sp3) P cross-coupling of alkyl substrates with P(O) H compounds and phosphites

Ligand-Free Iron-Catalyzed Construction of C–P Bonds via Phosphorylation of Alcohols: Synthesis of Phosphine Oxides and Phosphine Compounds

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Direct phosphorylation of benzylic C–H bonds under transition metal-free conditions forming sp3C–P bonds

Abstract: Direct phosphorylation of benzylic C–H bonds with secondary phosphine oxides was first realized. The reaction was performed in organo/aqueous biphasic system and under transition metal-free conditions, proceeding via the cross dehydrogenative coupling.

Cited by 3 publications

References 102 publications

Recent advances in electrochemical C—H phosphorylation

Recent advances in electrochemical C—H phosphorylation

C(sp3) P cross-coupling of alkyl substrates with P(O) H compounds and phosphites

Ligand-Free Iron-Catalyzed Construction of C–P Bonds via Phosphorylation of Alcohols: Synthesis of Phosphine Oxides and Phosphine Compounds

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Direct phosphorylation of benzylic C–H bonds under transition metal-free conditions forming sp³C–P bonds