Rhodium‐Catalyzed Synthesis of Dialkyl(Heteroaryl)Phosphine Sulfides by Phosphinylation of Heteroaryl Sulfides

Arisawa, Mieko; Tazawa, Takeru; Ichinose, Wataru; Kobayashi, Haruki; Yamaguchi, Masahiko

doi:10.1002/adsc.201800630

Cited by 9 publications

(5 citation statements)

References 29 publications

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“…It is expected that the obtained P V –S and P V –Se interelement compounds 19a and 20a will be promising synthetic reagents and intermediates for the syntheses of multifunctionalized organic molecules, − use in living polymerization processes, and trapping of radical species. − Although a number of synthetic methods for 19a , 20a , and their related derivatives have been reported, the majority involve ionic pathways, such as nucleophilic substitution using air- and moisture-sensitive phosphorus sources (e.g., Ph 2 P(S)–SH, Ph 2 P(S)–Cl). − Recently, a transition-metal-catalyzed route to synthesis of 19a and its related derivatives has also been reported …”

Section: Results and Discussionmentioning

confidence: 99%

“…26−34 Recently, a transition-metal-catalyzed route to synthesis of 19a and its related derivatives has also been reported. 35 However, no examples of radical methods for the preparation of P V −S and P V −Se interelement compounds have been reported, despite the fact that radical methods are generally advantageous in terms of their excellent tolerances to a wide variety of functional groups and solvents. The results obtained for the reactions outlined in eqs 2 and 3 strongly suggest that the photoinduced reaction between the air-and moisture-stable tetraphenyldiphosphine disulfide 1d and either diphenyl disulfide 9a or diselenide 12a may be a powerful tool to obtain P V −S and P V −Se interelement compounds.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Photoinduced Syntheses and Reactivities of Phosphorus-Containing Interelement Compounds

et al. 2020

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The photoinduced reactions of tetraphenyldiphosphine disulfide with a range of organic dichalcogenides successfully afforded a series of phosphorus(V)−chalcogen interelement compounds via a radical process. The relative reactivities of the organic dichalcogenides (i.e., (PhS) 2 , (PhSe) 2 , and (PhTe) 2 ) toward the P III or P V groups in the diphosphine analogues under light were investigated in detail, and a convenient method was developed to form P−S or P−Se interelement compounds from tetraphenyldiphosphine disulfide and (PhS) 2 or (PhSe) 2 upon photoirradiation. Furthermore, the relative photochemical properties and reactivities of tetraphenyldiphophine (P− P interelement compound) and its analogues toward photoinduced radical addition reactions were also discussed. The formed P−E (E = S, Se) interelement compounds could be utilized for ionic reactions, and they could be transformed into various phosphine reagents via one-pot processes.

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Section: Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Photoinduced Syntheses and Reactivities of Phosphorus-Containing Interelement Compounds

et al. 2020

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“…A rhodium catalyst promoted the cleavage of C-P bonds in heteroarylphosphine sulfides and exchange with disulfides (Scheme 18) [52]. When (2-benzothiazolyl) dimethylphosphine sulfide was reacted with dioctyl disulfide in the presence of RhH(PPh 3 ) 4 (10 mol%) and 1,2-bis (dimethylphosphino)benzene (dmppBz) (20 mol%) in refluxing chlorobenzene for 3 h, 2-(octylthio) benzothiazole was obtained in 46% yield.…”

Section: Scheme 17 Exchange Reaction Of Cyclopentaphosphine and Disumentioning

confidence: 99%

“…Rhodium-catalyzed insertion of 1-akynes may be applied to aliphatic disulfides, which are less reactive than aromatic disulfides (Scheme 19) [54]. The reverse reaction converts heteroaryl sulfides to heteroarylphosphine sulfides in the presence of diphosphine disulfides (Scheme 18) [52,53]. When 2-(p-tolylthio)-1,3-benzothiazole and tetraethyldiphosphine disulfides were reacted in refluxing chlorobenzene for 6 h in the presence of RhH(PPh3)4 (5 mol%) and 1,2-(diethylphosphino) ethane (depe) (10 mol%), 2-(diethylphosphino)-1,3benzothiazole sulfide was obtained in 49% yield.…”

Section: Rhodium-catalyzed Insertion Reactions Using Disulfidesmentioning

confidence: 99%

Rhodium-Catalyzed Synthesis of Organosulfur Compounds Involving S-S Bond Cleavage of Disulfides and Sulfur

Arisawa

Yamaguchi

2020

Molecules

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Organosulfur compounds are widely used for the manufacture of drugs and materials, and their synthesis in general conventionally employs nucleophilic substitution reactions of thiolate anions formed from thiols and bases. To synthesize advanced functional organosulfur compounds, development of novel synthetic methods is an important task. We have been studying the synthesis of organosulfur compounds by transition-metal catalysis using disulfides and sulfur, which are easier to handle and less odiferous than thiols. In this article, we describe our development that rhodium complexes efficiently catalyze the cleavage of S-S bonds and transfer organothio groups to organic compounds, which provide diverse organosulfur compounds. The synthesis does not require use of bases or organometallic reagents; furthermore, it is reversible, involving chemical equilibria and interconversion reactions.

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“…Thioesters were converted into dithiophosphinates under reflux in chlorobenzene, whilst various heterocyclic sulfides were converted into the corresponding heterocyclic phosphine sulfides under reflux in THF. 22 M. Arisawa The acyl exchange reaction between a phosphinoester and thioester is reversible in the presence of RhH(PPh 3 ) 4 and dppe under reflux in chlorobenzene, and achieves chemical equilibrium (Scheme 19). 23 For efficient conversion of acylphosphines into thioesters, treatment with disulfides provided thiophosphinates and thioesters via exothermic reactions.…”

Section: Scheme 16 Rhodium-catalyzed Metathesis Reactions Of Disulfidmentioning

confidence: 99%

Transition-Metal-Catalyzed Synthesis of Organophosphorus Compounds Involving P–P Bond Cleavage

Arisawa

2020

Synthesis

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Organophosphorus compounds are used as drugs, pesticides, detergents, food additives, flame retardants, synthetic reagents, and catalysts, and their efficient synthesis is an important task in organic synthesis. To synthesize novel functional organophosphorus compounds, transition-metal-catalyzed methods have been developed, which were previously considered difficult because of the strong bonding that occurs between transition metals and phosphorus. Addition reactions of triphenylphosphine and sulfonic acids to unsaturated compounds in the presence of a rhodium or palladium catalyst lead to phosphonium salts, in direct contrast to the conventional synthesis involving substitution reactions of organohalogen compounds. Rhodium and palladium complexes catalyze the cleavage of P–P bonds in diphosphines and polyphosphines and can transfer organophosphorus groups to various organic compounds. Subsequent substitution and addition reactions proceed effectively, without using a base, to provide various novel organophosphorus compounds.1 Introduction2 Transition-Metal-Catalyzed Synthesis of Phosphonium Salts by Addition Reactions of Triphenylphosphine and Sulfonic Acids3 Rhodium-Catalyzed P–P Bond Cleavage and Exchange Reactions4 Transition-Metal-Catalyzed Substitution Reactions Using Diphosphines4.1 Reactions Involving Substitution of a Phosphorus Group by P–P Bond Cleavage4.2 Related Substitution Reactions of Organophosphorus Compounds4.3 Substitution Reactions of Acid Fluorides Involving P–P Bond Cleavage of Diphosphines5 Rhodium-Catalyzed P–P Bond Cleavage and Addition Reactions6 Rhodium-Catalyzed P–P Bond Cleavage and Insertion Reactions Using Polyphosphines7 Conclusions

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Rhodium‐Catalyzed Synthesis of Dialkyl(Heteroaryl)Phosphine Sulfides by Phosphinylation of Heteroaryl Sulfides

Cited by 9 publications

References 29 publications

Photoinduced Syntheses and Reactivities of Phosphorus-Containing Interelement Compounds

Photoinduced Syntheses and Reactivities of Phosphorus-Containing Interelement Compounds

Rhodium-Catalyzed Synthesis of Organosulfur Compounds Involving S-S Bond Cleavage of Disulfides and Sulfur

Transition-Metal-Catalyzed Synthesis of Organophosphorus Compounds Involving P–P Bond Cleavage

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