ChemInform Abstract: Electron-Transfer Activation. Photocyanation of Tertiary Amines.

ChemInform ◽  
2010 ◽  
Vol 22 (47) ◽  
pp. no-no
Author(s):  
J. SANTAMARIA ◽  
M. T. KADDACHI ◽  
J. RIGAUDY
Keyword(s):  
Electron Transfer ◽  
Tertiary Amines

Diastereoselective Tandem Addition−Cyclization Reactions of Unsaturated Tertiary Amines Initiated by Photochemical Electron Transfer (PET)

2000 ◽  
Vol 65 (25) ◽  
pp. 8690-8703 ◽  
Author(s):  
Samuel Bertrand ◽  
Norbert Hoffmann ◽  
Stéphane Humbel ◽  
Jean Pierre Pete
Keyword(s):  
Electron Transfer ◽  
Tertiary Amines ◽  
Cyclization Reactions

scholarly journals Semiconductors as sensitisers for the radical addition of tertiary amines to electron deficient alkenes

2003 ◽  
Vol 5 (3) ◽  
pp. 175-182 ◽  
Author(s):  
Siniša Marinković ◽  
Norbert Hoffmann
Keyword(s):  
Electron Transfer ◽  
Organic Synthesis ◽  
Radical Reaction ◽  
Heterogeneous Photocatalysis ◽  
Radical Addition ◽  
Point Of View ◽  
Tertiary Amines ◽  
Radical Intermediate ◽  
Radical Chain ◽  
High Yields

Using heterogeneous photocatalysis, the radical addition of tertiary amines with electron deficient alkenes can be performed in high yields (up to 98%) and high facial diastereoselectivity. The photochemical induced electron transfer process initiates the radical chain reaction and inorganic semiconductors likeTiO2and ZnS were used. According to the proposed mechanism, the reaction takes place at the surface of the semiconductor and the termination step results from an interfacial electron transfer from the conduction band to the oxoallyl radical intermediate. Frequently, semiconductors are used for the mineralisation of organic compounds in wastewater. However, in this case, they are used in organic synthesis. The process can be performed in a convenient way and is particularly interesting from the ecological and economical point of view. No previous functionalization of the tertiary amines is necessary for C − C bond formation. Further on, the amines are used both as reactant and as solvent. The excess is recycled by distillation and the inexpensive sensitiser can be easily removed by filtration. In this way, products of high interest for organic synthesis are obtained by a diastereoselective radical reaction.

Sterically hindered aromatic compounds. XI. Spectral and product studies of the decomposition of N-nitrosoacetanilides

1982 ◽  
Vol 60 (5) ◽  
pp. 607-615 ◽  
Author(s):  
L. Ross C. Barclay ◽  
Julian M. Dust
Keyword(s):  
Electron Transfer ◽  
Aromatic Compounds ◽  
Diazonium Salts ◽  
Tertiary Amines ◽  
Nitroso Group ◽  
Electron Transfer Mechanism ◽  
Hydride Shift ◽  
Butyl Group ◽  
Spin Resonance

Decomposition of N-nitroso-2,4,6-tri-tert-butylacetanilide (1) in benzene forms products 2,4,6-tri-tert-butylphenyl acetate (3), 3-(3,5-di-tert-butylphenyl)-2-acetoxy-2-methylpropane (4), and hydrocarbons 3-(3,5-di-tert-butylphenyl)- and 1-(3,5-di-tert-butylphenyl)-2-methylpropene (5 and 6) explained by a reactive aryl cation (2), the rearranged products (4, 5, 6) originating from a 1,5-hydride shift from an orthotert-butyl group in 2. In contrast, decomposition of 1 in triethylamine forms products 1,3,5-tri-tert-butylbenzene (10), 2,4,6-tri-tert-butylacetanilide (15), and 2-(3,5-di-tert-butylphenyl)-2-methylpropanal oxime (13), expected of a free radical pathway. Electron spin resonance evidence is given for intermediates formed by rearrangement of the 2,4,6-tri-tert-butylphenyl radical and spin trapped by the nitroso group of 1. CIDNP and esr studies on the dediazoniation of N-nitrosoacetanilide and aniline in the presence of tertiary amines support the proposed electron transfer mechanism. The results are briefly discussed in terms of the role of steric effects and electron transfer in the dediazoniation of nitrosoacetanilides and diazonium salts.

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