Rhodium-Catalyzed Insertion Reaction of PhP Group of Pentaphenylcyclopentaphosphine with Acyclic and Cyclic Disulfides

Arisawa, Mieko; Sawahata, Kyosuke; Yamada, Tomoki; Sarkar, Debayan; Yamaguchi, Masahiko

doi:10.1021/acs.orglett.7b03825

Cited by 13 publications

(7 citation statements)

References 33 publications

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“…Mixing symmetrical electrophile diphenyl disulfide 6 and dimer 2 resulted in the formation of diazaphospholene phenyl sulfide 7 (Equation 3, Scheme ). Cleavage of the P–P bonds in pentaphenylcyclopentaphosphine with 6 was reported by Arisawa, Yamaguchi, and co‐workers, but that work required heat, and the use of a rhodium‐containing catalyst . Attempted formation of a phosphorus‐boron bond via reaction of 2 with diboranes 8a or 8b was unsuccessful under these conditions.…”

Section: Methodsmentioning

confidence: 98%

Functionalization of Bis‐Diazaphospholene P–P Bonds with Diverse Electrophiles

2020

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Phosphorus‐sp3 or ‐sp2 carbon bonds are readily formed by the reaction of bis‐diazaphospholenes with several classes of electrophiles. These reactions result in cleavage of the phosphorus–phosphorus bond and formation of functionalized diazaphospholenes. The reactions proceed rapidly, without catalysis. Experimental evidence with aryl and alkyl halides suggests the intermediacy of radicals in some cases, however other evidence suggests either radical or polar mechanisms may be operative for certain substrates, with a dependence on reaction conditions. In three cases, the product aryl diazaphospholenes have been shown to transfer the aryl substituent to electrophiles. These results reveal that diazaphospholene dimers are potent participants in radical chemistry with organic substrates at room temperature without requiring chemical initiators.

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Section: Methodsmentioning

confidence: 98%

Functionalization of Bis‐Diazaphospholene P–P Bonds with Diverse Electrophiles

2020

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“…Polyphosphines are compounds containing phosphorus atoms with two P-P bonds and one organic group, and they exhibit reactivities different from those of diphosphines, which contain phosphorus atoms with one P-P bond and two organic groups. Polyphosphines undergo substitution reactions with disulfides, which involve the exchange of P-P and S-S bonds (Scheme 17) [51]. Pentaphenylcyclopentaphosphine was reacted with dihexyl disulfide in the presence of RhH(dppe) 2 ( The reaction of hydrophilic disulfides and diphosphonates, which are also water-soluble, proceeds in water in the presence of RhCl3 (Scheme 16) [50].…”

Section: Scheme 17 Exchange Reaction Of Cyclopentaphosphine and Disumentioning

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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“…This methodology allowed the preparation of different S‐P(Ph)‐S containing heterocycles in moderate to excellent yields. [ 54 ]…”

Section: Reactivity Of Cyclic Oligophosphanesmentioning

confidence: 99%

Synthesis and Reactivity of Monocyclic Homoleptic Oligophosphanes

Wellnitz

Hering‐Junghans

2020

Eur J Inorg Chem

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This Minireview outlines the synthesis and reactivity of homoleptic, cyclic oligophosphanes, which have been known for more than 150 years. We will discuss a variety of (PR)n (n = 3,4,5,6) species and outline approaches towards their syntheses in the first part of this review. Then the unique reactivity of these inorganic ring systems will be discussed in detail with a focus on recent findings within the last 20 years. First ring expansion reactions will be described, which are mainly restricted to cyclotriphosphanes. Secondly, ring fragmentation will be highlighted, including phosphinidene transfer reactions. Furthermore, cyclooligophosphanes can be functionalized while retaining the parent ring structures. As oligophosphanes offer multiple donor sites, in a last part the coordination chemistry of these species is highlighted. We hope that this Minireview will spark further interest in this underexplored class of compounds as reagents in inorganic and organic synthesis, as well as the design of new P‐containing materials.

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Rhodium-Catalyzed Insertion Reaction of PhP Group of Pentaphenylcyclopentaphosphine with Acyclic and Cyclic Disulfides

Cited by 13 publications

References 33 publications

Functionalization of Bis‐Diazaphospholene P–P Bonds with Diverse Electrophiles

Functionalization of Bis‐Diazaphospholene P–P Bonds with Diverse Electrophiles

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

Synthesis and Reactivity of Monocyclic Homoleptic Oligophosphanes

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