Phosphonium Compounds. I. Elimination Reactions of 2-Cyanoethyl Phosphonium Salts. Asymmetric Phosphines and Alkylenediphosphines

Grayson, Martin; Keough, Patricia Tarpey; Johnson, Gerald A.

doi:10.1021/ja01527a014

Cited by 41 publications

(8 citation statements)

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“…Quaternary phosphonium salts containing a 2-cyanoethyl group react with a base releasing the corresponding tertiary phosphines though a retro-Michael reaction, instead of forming a phosphorane (Scheme 1B). [24] An initial optimization employing the conditions developed previously in this laboratory [20] validated that reaction of phosphine 3 a with diaryliodonium salt 2 a in MeCN under irradiation with a 6 W blue LED (400-410 nm) for 4 h at ambient temperature under an argon atmosphere and in the absent of any additives effectively afford the corresponding phosphonium salt 5 a in an 83% NMR yield. The reaction mixture was used in the next step without isolation of 5 a.…”

mentioning

confidence: 80%

“…To circumvent the problem observed we designed an indirect alternative method employing readily accessible (2‐cyanoethyl) diphenylphosphine ( 3 a ) [23] as a stable and easy‐to‐handle diphenylphosphine surrogate in the arylation reactions with diaryliodonium salts to obtain the desired product (Ph 3 P, 4 a ). Quaternary phosphonium salts containing a 2‐cyanoethyl group react with a base releasing the corresponding tertiary phosphines though a retro‐Michael reaction, instead of forming a phosphorane (Scheme 1B) [24] …”

Section: Methodsmentioning

confidence: 99%

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Catalyst‐Free Visible Light Mediated Synthesis of Unsymmetrical Tertiary Arylphosphines

Bugaenko

Карчава

2022

Adv Synth Catal

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Arylation of tertiary aryl and alkyl phosphines bearing 2-cyanoethyl group with aryl(mesityl)iodonium triflates under blue light irradiation followed by retro-Michael reaction of the in situ generated quaternary phosphonium salts initiated by DBU represent a novel efficient and general method for the preparation of distinctly substituted tertiary arylphosphines. An operationally simple, one-pot protocol features mild, transitionmetal-free conditions, high selectivity, broad functional group compatibility, as well as scalability and would be applied to substrates with different electronic and steric nature.

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confidence: 80%

Section: Methodsmentioning

confidence: 99%

Catalyst‐Free Visible Light Mediated Synthesis of Unsymmetrical Tertiary Arylphosphines

Bugaenko

Карчава

2022

Adv Synth Catal

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“…Thus, in the result of successive quaternizationdecomposition processes starting from either CEP 28 or alkylbis(2-cyanoethyl)phosphines 61 unsymmetrical dialkyl(2-cyanoethyl)phosphines were synthesized (Scheme 45) [66].…”

Section: Quaternization and Decomposition Of Phosphonium Saltsmentioning

confidence: 99%

“…By the application of , -dihaloalkanes in the reaction the synthesis of alkylene[bis-(2-cyanoethyl)phosphines] 62 can be carried out (Scheme 46) [66].…”

Section: Quaternization and Decomposition Of Phosphonium Saltsmentioning

confidence: 99%

“…Upon shorter chain length of the alkylene moiety the cleavage of the carbonphosphorus bond occurs. Thus, attempts to synthesize by such procedure ethylenebis(dimethylphosphine) from ethylene[bis(dimethyl-2-cyanoethyl)phosphonium]bromide resulted in dimethyl(2-cyanoethyl)phosphine 63 as a single reaction product (Scheme 47) [66].…”

Section: Quaternization and Decomposition Of Phosphonium Saltsmentioning

confidence: 99%

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Synthesis and Coordination Chemistry of Cyano-Substituted Phosphines

Odinets¹,

Vinogradova²,

Matveeva³

et al. 2005

COC

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Synthetic approaches to both linear and cyclic cyano-substituted phosphines (P~CN-phosphines) found an industrial application as catalyst precursors, pesticides, herbicides, flame retardants, precursors of aminophosphines etc., are reported. The main synthetic routes include reduction of P=O containing precursors, alkylation of silylphosphines and metal phosphides by halogenoalkyl(aryl)carbonitriles, phosphorylation of the latter ones, decomposition of phosphonium salts and hydrophosphination of cyano-substituted olefins proceeding under non-catalytical conditions and with use of metal complex catalysis. Merits and demerits of each approach are discussed. Phosphines bearing cyano function as an additional coordination site show diverse coordination behavior depending on the phosphine structure and nature of the metal. Four main types of complexes are observed, namely those with P-monodentate coordination, with N-monodentate coordination and complexes where bidentate coordination mode of P and N atoms is realized either at the single metal atom or of bridged type between two different metal atoms. Thus coordination behavior of such P~CN-ligands relative to transition and non-transition metals, structure features of the complexes obtained and their application in catalytic processes are discussed.

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Stereochemical Aspects of Phosphorus Chemistry

Gallagher

Jenkins

1968

Topics in Stereochemistry

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Phosphonium Compounds. I. Elimination Reactions of 2-Cyanoethyl Phosphonium Salts. Asymmetric Phosphines and Alkylenediphosphines

Cited by 41 publications

References 0 publications

Catalyst‐Free Visible Light Mediated Synthesis of Unsymmetrical Tertiary Arylphosphines

Catalyst‐Free Visible Light Mediated Synthesis of Unsymmetrical Tertiary Arylphosphines

Synthesis and Coordination Chemistry of Cyano-Substituted Phosphines

Stereochemical Aspects of Phosphorus Chemistry

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