Photoinduced ligand-to-iron charge transfer enabled C(sp<sup>3</sup>)–H phosphorylation of hydrocarbons

Shi, Wei; Zhong, Ping-Fu; Qi, Xu-Kuan; Yang, Chao; Guo, Lin; Xia, Wujiong

doi:10.1039/d3gc02469e

Cited by 16 publications

(1 citation statement)

References 81 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Very recently, Xia's group described the development of an Fe-catalyzed C(sp 3 )−H phosphorylation based on a reductive SET between a radical and an [Fe(II)] complex (Scheme 33c). 309 This reaction exhibited a remarkably broad substrate scope that included various alkanes, halides, ketones and esters.…”

Section: Radical Substitution Of Fe Complexesmentioning

confidence: 99%

Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Wang,

He,

Wang

et al. 2024

Chem. Rev.

View full text Add to dashboard Cite

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) are Earth-abundant and can be employed to regulate radical C–H functionalization. The use of such metals is desirable because of the diverse interaction modes between first-row transition metal complexes and radical species including radical addition to the metal center, radical addition to the ligand of metal complexes, radical substitution of the metal complexes, single-electron transfer between radicals and metal complexes, hydrogen atom transfer between radicals and metal complexes, and noncovalent interaction between the radicals and metal complexes. Such interactions could improve the reactivity, diversity, and selectivity of radical transformations to allow for more challenging radical C–H functionalization reactions. This review examines the achievements in this promising area over the past decade, with a focus on the state-of-the-art while also discussing existing limitations and the enormous potential of high-value radical C–H functionalization regulated by these metals. The aim is to provide the reader with a detailed account of the strategies and mechanisms associated with such functionalization.

show abstract

Section: Radical Substitution Of Fe Complexesmentioning

confidence: 99%

Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Wang,

He,

Wang

et al. 2024

Chem. Rev.

View full text Add to dashboard Cite

show abstract

Photoinduced C−O Bond Formation through C−C Bond Cleavage of Alcohols by Suppressing Alcohol Oxidation

Wu,

2024

Adv Synth Catal

View full text Add to dashboard Cite

Herein, we present a photoinduced deconstructive alkoxyamination of alkyl alcohols catalyzed by iron salts. This transformation involves the initiation of alkoxy radicals through chlorine radical‐induced alkoxy radical formation, followed by β‐scission and trapping of the resulting carbon radicals with 2,2,6,6‐tetramethylpiperidin‐1‐yl (TEMPO). This reaction exhibits a broad substrate scope (40 examples), including primary and secondary alcohols that are prone to oxidation by the combination of TEMPO and iron. Mechanistic investigations have revealed that enhanced coordination of the chloride ion with the iron center inhibits the OH oxidation process, thereby enabling the tolerance of primary and secondary alcohols.

show abstract

Benzylic C(sp³)−H Phosphonylation via Dual Photo and Copper Catalysis

Li,

Liu,

Kramer

2024

Angewandte Chemie

View full text Add to dashboard Cite

Alkyl phosphonates are important motifs in medicinal chemistry, yet their efficient synthesis by direct C(sp3)–H functionalization remains a challenge. Here, we report straightforward access to benzylic phosphonates by direct C(sp3)–H functionalization in a cross‐dehydrogenative‐coupling reaction between non‐specialized alkylarenes and unfunctionalized phosphites. Notably, the C–H substrates are used as the limiting reagents. The scope of benzylic C–H substrates is broad, and the mild reaction conditions allow for good functional group tolerance. Mechanistic studies indicate that the reaction proceeds via a radical pathway rather than the cationic pathway followed for specialized benzylic C–H substrates in previous methods.

show abstract

Photoinduced ligand-to-iron charge transfer enabled C(sp³)–H phosphorylation of hydrocarbons

Abstract: Organophosphine compounds are of high significance in organic synthesis, organometallic chemistry, and material science. The high demand for the incorporation of phosphine moieties into molecular structures has witnessed significant progress....

Cited by 16 publications

References 81 publications

Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Photoinduced C−O Bond Formation through C−C Bond Cleavage of Alcohols by Suppressing Alcohol Oxidation

Benzylic C(sp³)−H Phosphonylation via Dual Photo and Copper Catalysis

Contact Info

Product

Resources

About

Photoinduced ligand-to-iron charge transfer enabled C(sp3)–H phosphorylation of hydrocarbons

Abstract: Organophosphine compounds are of high significance in organic synthesis, organometallic chemistry, and material science. The high demand for the incorporation of phosphine moieties into molecular structures has witnessed significant progress....

Cited by 16 publications

References 81 publications

Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Photoinduced C−O Bond Formation through C−C Bond Cleavage of Alcohols by Suppressing Alcohol Oxidation

Benzylic C(sp3)−H Phosphonylation via Dual Photo and Copper Catalysis

Contact Info

Product

Resources

About

Photoinduced ligand-to-iron charge transfer enabled C(sp³)–H phosphorylation of hydrocarbons

Benzylic C(sp³)−H Phosphonylation via Dual Photo and Copper Catalysis