Isocyanide reductions. A convenient method for deamination

Niznik, G. E.; Walborsky, H. M.

doi:10.1021/jo00406a020

Cited by 32 publications

(9 citation statements)

References 2 publications

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“…This reaction looks unusual since, to the best of our knowledge, no example of decyanation of isonitrile on transition metals has been previously reported. Reduction of isonitriles has been performed by using sodium−liquid ammonia or sodium naphthalene solutions or, alternatively, by using organotin hydrides in the presence of catalytic amounts of AIBN . However, the isomerization of isocyanide into nitriles is known to occur spontaneously at high temperature, and a few examples of catalytic decyanation and of oxidative addition of nitriles to low-valent transition complexes are known.…”

Section: Resultsmentioning

confidence: 99%

Hydride and Dihydrogen Ruthenium Complexes of the Tripyrrolylphosphine Ligand

et al. 1998

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The reactivity of the ruthenium(IV) trihydride complex Cp*RuH3(Ppyl3) (2), accommodating the π-accepting tripyrrolylphosphine (Ppyl3), has been studied with regard to substitution and protonation reactions. Substitution of two hydrides by excess Ppyl3 and CO leads to Cp*RuHL(Ppyl3) (L = Ppyl3, 3; L = CO, 4). The reaction with tBuNC leads first to the substitution of two hydrides by the ligand, but the reaction proceeds further to yield, through an unprecedented decyanation reaction, the cyano complex Cp*Ru(CN)(tBuNC)(Ppyl3) (6), which has been characterized by X-ray diffraction. Addition of HSiMe2Ph in refluxing toluene yields Cp*RuH2(SiMe2Ph)(Ppyl3) (7), a dihydridosilylruthenium(IV) complex that has been characterized by spectroscopic data and an X-ray crystal structure. Finally, protonation of 4 yields the dihydrogen complex [Cp*Ru(H2)(CO)(Ppyl3)](BF4) (8), which easily loses H2 in solution and displays a very short T 1 minimum, in agreement with a low electron density on the metal.

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Section: Resultsmentioning

confidence: 99%

Hydride and Dihydrogen Ruthenium Complexes of the Tripyrrolylphosphine Ligand

et al. 1998

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“…The single electron reduction of isonitriles has been previously proposed using sodium naphthalene as reductant. [50] However, no data is available in the literature on the redox potential of these compounds. We tried to measure the reduction potential of tert-butyl isonitrile using cyclic voltammetry.…”

Section: Methodsmentioning

confidence: 99%

“…The radical anion generated upon reduction of the isonitrile could undergo β-fragmentation to generate a carbon-centered radical and a cyanide anion, similar to that proposed using sodium naphthalene. [50] Once the carboncentered radical is formed, it could then react with the silane through hydrogen atom transfer to provide the deamination product. The silyl radical generated after HAT could be oxidized by 4CzIPN * + to a silyl cation [51] eventually trapped by the cyanide anion, regenerating the ground-state catalyst.…”

Section: Methodsmentioning

confidence: 99%

Isonitriles as Alkyl Radical Precursors in Visible Light Mediated Hydro‐ and Deuterodeamination Reactions**

Quirós,

Martín,

Gomez‐Mendoza

et al. 2024

Angew Chem Int Ed

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Herein, we report the use of isonitriles as alkyl radical precursors in light‐mediated hydro‐ and deuterodeamination reactions. The reaction is scalable, shows broad functional group compatibility and potential to be used in late‐stage functionalization. Importantly, the method is general for Cα‐primary, Cα‐secondary and Cα‐tertiary alkyl isonitriles. For most examples, high yields were obtained through direct visible‐light irradiation of the isonitrile in the presence of a silyl radical precursor. Interestingly, in the presence of an organic photocatalyst (4CzIPN) a dramatic acceleration was observed. In‐depth mechanistic studies using UV‐vis absorption, steady‐state and time‐resolved photoluminescence, and transient absorption spectroscopy suggest that the excited state of 4CzIPN can engage in a single‐electron transfer with the isonitrile.

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“…Many other reagents, including phosgene [ 20 ], diphosgene (trichloromethyl carbonochloridate) [ 21 ], organic chlorophosphate derivatives [ 22 ], XtalFluor-E [ 23 ], tosyl chloride [ 24 ], and phosphoryl chloride [ 19 , 25 ] have been employed as dehydrating reagents in combination with bases, most commonly tertiary amines, to avoid reduced yields of the products. However, all advances have one or more flaws, such as lengthy, tedious operations, exotic and expensive reagents, enormous waste generation, and prolonged exposure of the chemist to potentially toxic gases, and they frequently have a limited functionalization scope [ 15 , 25 , 26 , 27 ].…”

Section: Introductionmentioning

confidence: 99%

A More Sustainable Isocyanide Synthesis from N-Substituted Formamides Using Phosphorus Oxychloride in the Presence of Triethylamine as Solvent

Salami

Siwe‐Noundou²,

Krause³

2022

Molecules

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A simple, green, and highly efficient protocol for the synthesis of isocyanides is described. The reaction involves dehydration of formamides with phosphorus oxychloride in the presence of triethylamine as solvent at 0 °C. The product isocyanides were obtained in high to excellent yields in less than 5 min. The method offers several advantages including increased synthesis speed, relatively mild conditions, and rapid access to large numbers of functionalized isocyanides, excellent purity, increased safety, and minimal reaction waste. The new approach of synthesising dehydrative isocyanides from formamides is significantly more environmentally-friendly than prior methods.

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Isocyanide reductions. A convenient method for deamination

Cited by 32 publications

References 2 publications

Hydride and Dihydrogen Ruthenium Complexes of the Tripyrrolylphosphine Ligand

Hydride and Dihydrogen Ruthenium Complexes of the Tripyrrolylphosphine Ligand

Isonitriles as Alkyl Radical Precursors in Visible Light Mediated Hydro‐ and Deuterodeamination Reactions**

A More Sustainable Isocyanide Synthesis from N-Substituted Formamides Using Phosphorus Oxychloride in the Presence of Triethylamine as Solvent

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