Chemoselectivity of the reactions of haloacetonitriles with hydrogen phosphonates: the dramatic effect of the nature of the halogen atom

Rassukana, Yuliya V.; Yelenich, Ivanna P.; Bezdudny, Andrii V.; Миронов, В. Ф.; Onys’ko, P. P.

doi:10.1016/j.tetlet.2014.07.017

Cited by 11 publications

(6 citation statements)

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“…6 This class of compounds was first synthesized in 1971 via the reaction of acetonitrile with phosphorus(III) bromide mediated by a strong acid. 5 Currently, these compounds are produced by hydrophosphorylation (addition of H−P(O)(OR) 2 ) of nitriles 7 and isonitriles 8 in the presence of acid 7b or base. 9 The viability of this reaction protocol is linked to the high acidity of phosphonates (pK a ≈ 18.4−9.0).…”

Section: ■ Introductionmentioning

confidence: 99%

Lanthanum-Catalyzed Double Hydrophosphinylation of Nitriles

Basiouny

Schmidt

2017

Organometallics

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A new lanthanum-based catalyst was shown to be effective for the double hydrophosphinylation of unactivated nitriles under very mild conditions. Surprisingly, the lanthanum catalyst gave two regioisomeric products depending on the nature of the starting nitrile. Primary alkyl nitriles undergo 1,1-addition to give products with a new P–C–P linkage and concomitant formation of a primary amine. Under the same conditions, secondary alkyl and aryl nitriles instead produced 1,2-addition products, where 1 equiv of the phosphine oxide was added to the carbon, while a second equivalent added to the nitrogen of the nitrile, resulting in a P–C–N–P framework. Further investigation of the catalytic cycle yielded evidence that all nitriles first undergo 1,1-addition (deemed the kinetic product) that then undergoes isomerization to the final unsymmetric addition product (the thermodynamic product). All catalytic reactions were run neat or with very little solvent, required little workup, and had high to moderate yields.

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Section: ■ Introductionmentioning

confidence: 99%

Lanthanum-Catalyzed Double Hydrophosphinylation of Nitriles

Basiouny

Schmidt

2017

Organometallics

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“…The reaction protocol of dialkylphosphites to trihaloacetonitriles catered two alternate pathways as illustrated in scheme 2. 46 Trifluoroacetonitriles provided iminophosphonates as displayed in route (a), which drastically tuned to route (b) forming dichloro-acetonitrile and the equivalent chlorophosphate on replacing the fluorine atoms in trifluoroacetonitrile with the chlorine atoms.…”

Section: P-h Bond Addition To Organic Nitrilesmentioning

confidence: 99%

Recent advances in the carbon–phosphorus (C–P) bond formation from unsaturated compounds by s- and p-block metals

Banerjee

Panda

2021

Org. Biomol. Chem.

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“…133 A series of trihaloacetonitriles, bearing a different number of fluorine and chlorine atoms in the molecule, were also investigated in the above reaction. 134 Scheme 117. Formation of imidoyl phosphonates 282 and 283, and geminal bisphosphonates 284 and 285.…”

Section: Scheme 114 Synthesis Of Monofluorinated α-Aminonitrile N147 and Fluoroamine 266mentioning

confidence: 99%

Chemistry of fluoroalkyl cyanides

Usachev¹

2020

Arkivoc

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This review is devoted to the chemistry of fluoroalkyl cyanides (R F -nitriles): their synthesis and chemical properties. Syntheses of non-functionalized R F -nitriles (FCH 2 CN, F 2 CHCN, CF 3 CN, C 2 F 5 CN, FCH 2 CH 2 CN, etc.) and dinitriles (NCCHFCN, NCCF 2 CN, NCCF 2 CF 2 CN, etc.) are considered. The synthesis of functionalized R F -nitriles such as F 2 NCF 2 CN, F 2 NCClFCN, Cl 2 CFCN, Br 2 CFCN, (O 2 N) 2 CFCN, O 2 NCF 2 CH 2 CH 2 CN, and dinitriles, such as O(CF 2 CN) 2 , NCCF 2 N=NCF 2 CN, is also considered. R F -Nitriles are attractive electrophilic, enophilic, and dienophilic building-blocks: they were used in the synthesis of various fluorine-containing heterocyclic compounds, such as R F -bearing pyridines, 1,3,5-triazines, tetrazoles, and others. R F -nitriles were also used in the synthesis of unusual acyclic compounds, such as fluoroalkylated N,N-difluoroamines, F 2 NCF 2 CF 2 N=SF 2 , R Fimino esters, and others.

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Chemoselectivity of the reactions of haloacetonitriles with hydrogen phosphonates: the dramatic effect of the nature of the halogen atom

Cited by 11 publications

References 11 publications

Lanthanum-Catalyzed Double Hydrophosphinylation of Nitriles

Lanthanum-Catalyzed Double Hydrophosphinylation of Nitriles

Recent advances in the carbon–phosphorus (C–P) bond formation from unsaturated compounds by s- and p-block metals

Chemistry of fluoroalkyl cyanides

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