Isonitriles as source and fate of imidoyl radicals: a novel homolytic α-fragmentation

Nanni, Daniele; Pareschi, Patrizia; Tundo, A.

doi:10.1016/s0040-4039(97)82958-9

Cited by 30 publications

(8 citation statements)

References 23 publications

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“…The formation of minor unexpected regioisomeric product 3' was suggested to proceed through path b, in which radical B undergoes ipso cyclization; subsequently CÀN bond cleavage and aromatization leads to rearranged radical F. [22] The cyclohexadienyl radical intermediate F ultimately afforded quinoline 3' in a similar process as described in path a.…”

Section: ] (Ppy= 2-phenylpyridine) [Ru-mentioning

confidence: 95%

Visible‐Light‐Induced Radical Cyclization of Trifluoroacetimidoyl Chlorides with Alkynes: Catalytic Synthesis of 2‐Trifluoromethyl Quinolines

Dong

Liu

et al. 2013

Chemistry A European J

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Section: ] (Ppy= 2-phenylpyridine) [Ru-mentioning

confidence: 95%

Visible‐Light‐Induced Radical Cyclization of Trifluoroacetimidoyl Chlorides with Alkynes: Catalytic Synthesis of 2‐Trifluoromethyl Quinolines

Dong

Liu

et al. 2013

Chemistry A European J

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“…(1), R 2 = t-Bu], a process that has already been suggested as feasible, at least when the attacking (or released) species has fair stability. 23,24 To test the viability of this hypothesis DFT computations, B3LYP variant, were implemented using the Jaguar software suite 25 for a series of model imidoyl radicals. The results (Table 3) showed that β-scission was exothermic for t-BuN᎐ ᎐ C ؒ Bu-t and only mildly endothermic for t-BuN᎐ ᎐ C ؒ Ph and even for MeN᎐ ᎐ C ؒ Me.…”

Section: Methodsmentioning

confidence: 99%

An electron paramagnetic resonance study of intermediates generated from aromatic aldiminesElectronic supplementary information (ESI) available: Gaussian98 or Jaguar optimised structures for precursor imines and imidoyl radicals together with their energies at all levels of theory. See http://www.rsc.org/suppdata/p2/b2/b201682f/

Nanni

Pareschi

Walton

2002

J. Chem. Soc., Perkin Trans. 2

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It was shown by EPR spectroscopy that N-aryl-imines undergo hydrogen atom abstraction by tert-butoxyl radicals to generate imidoyl radicals in competition with addition to the C᎐ ᎐ N double bond to generate aminyl radicals. The latter were subsequently oxidised to nitroxides (aminoxyls) and also fragmented to release tert-butyl radicals and iminyl ethers. The main products identified were imines formed by combination of the imidoyl radicals with other radicals in the system. Thus, hydrogen abstraction is probably the most important homolytic pathway for the precursor imines. A similar reactivity pattern was found for N-tert-butyl-imines. DFT computations (B3LYP with a 6-31G* basis set) indicated that α-scissions of imidoyl radicals, ArN᎐ ᎐ C ؒ R (R = t-Bu or Me), to produce isonitriles, ArNC, were too endothermic to occur under the present experimental conditions. tert-Butoxyl radicals were shown to add to 1-isocyano-4-chlorobenzene to generate N-arylimidoyl radicals that fragmented to afford 4-chloro-1isocyanatobenzene.

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“…[39][40][41][42][43][44][45][46][47] In recent years, oxime derivatives have found broad applications as precursors of iminyl radicals generated by NÀ O bond cleavage. Other approaches to iminyl radicals, such as radical addition to isonitriles [48][49][50] or vinyl azides, [51][52][53][54][55][56][57][58] are useful for specific radical structure types. The oxime-based strategy allows for generation of diverse iminyl radicals from widely available carbonyl compounds that can be easily transformed into oximes.…”

Section: Introductionmentioning

confidence: 99%

Oxime‐Derived Iminyl Radicals in Selective Processes of Hydrogen Atom Transfer and Addition to Carbon‐Carbon π‐Bonds

et al. 2021

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Oximes represent one of the fundamental organic compound classes with a wide range of synthetic applications. In the last decade O-substituted oximes were recognized as the synthetically available and versatile precursors of iminyl radicals via one-electron oxidation or one-electron reduction employing visible light photoredox catalysts, salts of abundant metals (such as Cu or Fe), or other convenient reagents. Iminyl radicals are powerful synthons for various processes of cyclization, ringopening, CH-functionalization, and coupling. The present review is focused on the synthetic methods based on oxime-derived iminyl radicals developed in the last few years excluding ring opening reactions of cyclic iminyl radicals that were summarized in recent publications. The review consists of two main parts:(1) reactions of iminyl radicals involving 1,n-hydrogen atom transfer (n = 5 in most cases) and (2) reactions involving the addition of iminyl radical to the carbon-carbon π-bond.

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Isonitriles as source and fate of imidoyl radicals: a novel homolytic α-fragmentation

Cited by 30 publications

References 23 publications

Visible‐Light‐Induced Radical Cyclization of Trifluoroacetimidoyl Chlorides with Alkynes: Catalytic Synthesis of 2‐Trifluoromethyl Quinolines

Visible‐Light‐Induced Radical Cyclization of Trifluoroacetimidoyl Chlorides with Alkynes: Catalytic Synthesis of 2‐Trifluoromethyl Quinolines

Oxime‐Derived Iminyl Radicals in Selective Processes of Hydrogen Atom Transfer and Addition to Carbon‐Carbon π‐Bonds

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