Phosphorylation of C(sp<sup>3</sup>)–H Bonds via 1,4-Palladium Migration

Ji, Xiaoming; Chen, Yanzhen; Fu, Jian‐Guo; Zhang, Shusheng; Feng, Chen‐Guo

doi:10.1021/acs.orglett.2c01303

Cited by 16 publications

(2 citation statements)

References 31 publications

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“…The formation of methyl ortho ‐ tert ‐butyl‐ trans ‐cinnamate 4 clearly suggested that the palladium species migrate from neophentyl carbon center to ortho ‐position of the phenyl ring (from 5 to 6 ). Later, this “through space” palladium/hydrogen migration process has been proved to be quite general by studies from the research groups of Larock, [4b–c] Zhu, [4e] Baudoin, [4f–i] Feng [4j–o] and et al [4n–r] . Mechanistically, the migration was proposed to take place through the formation of a five‐membered palladacycle, which could further undergo reductive elimination or protonation to generate the rearranged palladium species (Scheme 1b).…”

Section: Introductionmentioning

confidence: 98%

Taming the Selective C−H Bond Activation through 1,5‐Palladium Migration

Fang,

Ding,

Huang

2024

ChemCatChem

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“Through space” metal/hydrogen shift constitutes one of the efficient elementary step in organometallic chemistry to achieve selective remote C‐H bond functionalization. Compared with the relatively extensive exploration on 1,4‐palladium migration, the processes on corresponding 1,5‐palladium translocation are far less explored. Based on our understanding on related research areas, we summarized the advances achieved on remote C‐H bond activation through a key step of 1,5‐palladium migration in this minireview. The background, reaction scope, and more importantly, the mechanistic rationale of each transformation was discussed. We hope by reading through this minireview, one could get a general perspective on direct C‐H bond activation via 1,5‐palladium/hydrogen shift, and could understand why such a process is less common when compared with the process going through 1,4‐palladium/hydrogen migration, and eventually could be inspired to develop practical ways for the synthesis of valuable molecules, which could not be prepared easily through other traditional approach.

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Section: Introductionmentioning

confidence: 98%

Taming the Selective C−H Bond Activation through 1,5‐Palladium Migration

Fang,

Ding,

Huang

2024

ChemCatChem

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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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Alkyne Insertion Enabled Vinyl to Acyl 1,5‐Palladium Migration: Rapid Access to Substituted 5‐Membered‐Dihydrobenzofurans and Indolines

Ding

et al. 2023

Angewandte Chemie

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“Through space” palladium/hydrogen shift is an efficient strategy to achieve selective functionalization of a specific remote C−H bond. Compared with relatively extensive exploited 1,4‐palladium migration process, the relevant 1,5‐Pd/H shift was far less investigated. We herein report a novel 1,5‐Pd/H shift pattern between a vinyl and an acyl group. Through the pattern, rapid access to 5‐membered‐dihydrobenzofuran and indoline derivatives has been achieved. Further studies have unveiled an unprecedented trifunctionalization (vinylation, alkynylation and amination) of a phenyl ring through 1,5‐palladium migration relayed decarbonylative Catellani type reaction. A series of mechanistic investigations and DFT calculations have provided insights into the reaction pathway. Notably, it was unveiled that the 1,5‐palladium migration in our case prefers a stepwise mechanism involving a PdIV intermediate.

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Phosphorylation of C(sp³)–H Bonds via 1,4-Palladium Migration

Cited by 16 publications

References 31 publications

Taming the Selective C−H Bond Activation through 1,5‐Palladium Migration

Taming the Selective C−H Bond Activation through 1,5‐Palladium Migration

Recent advances in electrochemical C—H phosphorylation

Alkyne Insertion Enabled Vinyl to Acyl 1,5‐Palladium Migration: Rapid Access to Substituted 5‐Membered‐Dihydrobenzofurans and Indolines

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Phosphorylation of C(sp3)–H Bonds via 1,4-Palladium Migration

Cited by 16 publications

References 31 publications

Taming the Selective C−H Bond Activation through 1,5‐Palladium Migration

Taming the Selective C−H Bond Activation through 1,5‐Palladium Migration

Recent advances in electrochemical C—H phosphorylation

Alkyne Insertion Enabled Vinyl to Acyl 1,5‐Palladium Migration: Rapid Access to Substituted 5‐Membered‐Dihydrobenzofurans and Indolines

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Phosphorylation of C(sp³)–H Bonds via 1,4-Palladium Migration