Applications of Diphosphines in Radical Reactions

Kawaguchi, Shin‐ichi

doi:10.1002/ajoc.201900339

Cited by 14 publications

(9 citation statements)

References 52 publications

(30 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In 2019, Kawaguchi and Ogawa reported an application of TMDPO to prepare perfluoroalkylphosphines in trifluorotoluene (BTF) under UV light 134 (Scheme 55). The mechanism of this elegant work relied on the radical substitution between a photogenerated phosphinoyl radical and a perfluoroalkyl halide.…”

Section: Figure 7 Examples Of Bis-acylphosphine Oxides Used As Photoimentioning

confidence: 99%

Shining Light on the Light-Bearing Element: A Brief Review of Photomediated C–H Phosphorylation Reactions

Ung¹,

Mechrouk²,

Li³

2020

Synthesis

View full text Add to dashboard Cite

Organophosphorus compounds have numerous useful applications, from versatile ligands and nucleophiles in the case of trivalent organophosphorus species to therapeutics, agrochemicals and material additives for pentavalent species. Although phosphorus chemistry is a fairly mature field, the construction of C–P(V) bonds relies heavily on either prefunctionalized substrates such as alkyl or aryl halides, or requires previously oxidized bonds such as C=N or C=O, leading to potential sustainability issues when looking at the overall synthetic route. In light of the recent advances in photochemistry, using photons as a reagent can provide better alternatives for phosphorylations by unlocking radical mechanisms and providing interesting redox pathways. This review will showcase the different photomediated phosphorylation procedures available for converting C–H bonds into C–P(V) bonds.1 Introduction1.1 Organophosphorus Compounds1.2 Phosphorylation: Construction of C–P(V) Bonds1.3 Photochemistry as an Alternative to Classical Phosphorylations2 Ionic Mechanisms Involving Nucleophilic Additions3 Mechanisms Involving Radical Intermediates3.1 Mechanisms Involving Reactive Carbon Radicals3.2 Mechanisms Involving Phosphorus Radicals3.2.1 Photoredox: Direct Creation of Phosphorus Radicals3.2.2 Photoredox: Indirect Creation of Phosphorus Radicals3.2.3 Dual Catalysis3.3 Photolytic Cleavage4 Conclusion and Outlook

show abstract

Section: Figure 7 Examples Of Bis-acylphosphine Oxides Used As Photoimentioning

confidence: 99%

Shining Light on the Light-Bearing Element: A Brief Review of Photomediated C–H Phosphorylation Reactions

Ung¹,

Mechrouk²,

Li³

2020

Synthesis

View full text Add to dashboard Cite

show abstract

“…The radical addition reactions of halogens and organic disulfides have been reported to occur under photoirradiation, but their synthetic applications are limited. To clarify the universality of the photoinduced radical reaction of heteroatom compounds as a method for generating carbon-heteroatom bonds, we previously investigated a series of radical addition reactions to the carbon-carbon unsaturated bonds, of group 16 (e.g., diselenides and ditellurides) [32][33][34][35][36], group 15 (e.g., diphosphines) [37][38][39][40][41][42], and group 13 (e.g., diboranes) compounds [43,44]. We then combined these reactions with disulfides and fluorinated iodoalkanes and successfully formed a variety of carbon-heteroatom bonds [45][46][47][48][49][50][51][52][53].…”

Section: Introductionmentioning

confidence: 99%

Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization

et al. 2022

Self Cite

View full text Add to dashboard Cite

The addition of interelement compounds with heteroatom-heteroatom single bonds to carbon-carbon unsaturated bonds under light irradiation is believed to be an atomically efficient method to procure materials with carbon-heteroatom bonds. In this study, we achieved the photoinduced bisphosphination of alkynes using the phosphorus interelement compound, tetraphenyldiphosphine monosulfide (1), to stereoselectively obtain the corresponding (E)-vic-1,2-bisphosphinoalkenes, which are important transition-metal ligands. The bisphosphination reaction was performed by mixing 1 and various alkynes and then exposing the mixture to light irradiation. Optimization of the conditions for the bisphosphination reaction resulted in a wide substrate range and excellent trans-selectivity. Moreover, the completely regioselective introduction of pentavalent and trivalent phosphorus groups to the terminal and internal positions of the alkynes, respectively, was achieved. We also found that the novel double-bond isomerization reaction of the synthesized bisphosphinated products occurred with a catalytic amount of a base under mild conditions. Our method for the photoinduced bisphosphination of carbon-carbon unsaturated compounds may have strong implications for both organic synthesis and organometallic and catalyst chemistry.

show abstract

“…The nucleophilic substitution reaction of 1, n -dihalogenated alkanes with highly reactive metal phosphides is the classical but reliable synthetic approach to the aforementioned compounds . On the other hand, given the recent progress of phosphinative difunctionalization reactions of alkenes such as carbophosphination, aminophospination, and cyanophosphination, the diphosphination reaction of alkynes and/or alkenes with diphosphines (R 2 P–PR 2 ) is also considered to be more attractive owing to its potentially better efficiency. , In 2005, Oshima and Yorimitsu reported the V-40-initiated radical diphosphination of terminal alkynes with diphosphines . Ogawa also developed the same radical diphosphination under UV irradiation .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of DPPP- and DPPPEN-Type Bidentate Ligands by Ring-Opening Diphosphination of Methylene- and Vinylcyclopropanes under Visible-Light-Promoted Photoredox Catalysis

et al. 2020

View full text Add to dashboard Cite

A ring-opening diphosphination of methylene-and vinylcyclopropanes with tetraaryldiphosphines (Ar 2 P−PAr 2 ) has been developed to afford the corresponding 1,3-diphenylphosphinopropane-and 1,3-diphenylphosphinopentane-type bidentate ligands, respectively. The reaction proceeds under bromine cation-initiated, visible-light-promoted photoredox catalysis at ambient temperature. Owing to the ready availability of functionalized diphosphines, the electronically diverse MeO-and CF 3 -substituted bidentate ligands are also easily prepared.

show abstract

Applications of Diphosphines in Radical Reactions

Cited by 14 publications

References 52 publications

Shining Light on the Light-Bearing Element: A Brief Review of Photomediated C–H Phosphorylation Reactions

Shining Light on the Light-Bearing Element: A Brief Review of Photomediated C–H Phosphorylation Reactions

Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization

Synthesis of DPPP- and DPPPEN-Type Bidentate Ligands by Ring-Opening Diphosphination of Methylene- and Vinylcyclopropanes under Visible-Light-Promoted Photoredox Catalysis

Contact Info

Product

Resources

About