Visible-Light-Mediated Synthesis of Amidyl Radicals: Transition-Metal-Free Hydroamination and N-Arylation Reactions
The development of photoredox reactions of aryloxy-amides for the generation of amidyl radicals and their use in hydroamination-cyclization and N-arylation reactions is reported. Owing to the ease of single-electron-transfer reduction of the aryloxy-amides, the organic dye eosin Y was used as the photoredox catalyst, which results in fully transition-metal-free processes. These transformations exhibit a broad scope, are tolerant to several important functionalities, and have been used in the late-stage modification of complex and high-value N-containing molecules.
Davies, Jacob,Svejstrup, Thomas D.,Fernandez Reina, Daniel,Sheikh, Nadeem S.,Leonori, Daniele
supporting information
p. 8092 - 8095
(2016/07/16)
A new source of nitrogen centered radicals
Exposure of thiocarbazone derivatives 6b-10b, 11c-13c, and 14a-15a to tributylstannane in the presence of AIBN leads to various nitrogen centered radicals which are easily captured by an internal olefin.
Callier-Dublanchet, Anne-Claude,Quiclet-Sire, Beatrice,Zard, Samir Z.
p. 8791 - 8794
(2007/10/02)
Iminyl, Amidyl, and Carbamyl Radicals from O-Benzoyl Oximes and O-Benzoyl Hydroxamic Acid Derivatives.
Oxime benzoates and O-benzoyl hydroxamic acid derivatives react with tributylstannane in the presence of AIBN to give iminyl, amidyl, and carbamyl radicals which can be captured by an internal olefin.
Boivin, Jean,Callier-Dublanchet, Anne-Claude,Quiclet-Sire, Beatrice,Schiano, Anne-Marie,Zard, Samir Z.
p. 6517 - 6528
(2007/10/02)
Amidyl and Carbamyl Radicals by Stannane Mediated Cleavage of O-Benzoyl Hydroxamic Acid Derivatives.
O-Benzoyl hydroxamic acids react with tributylstannane in the presence of AIBN to give amidyl or carbamyl radicals which can be captured by an internal olefin.
Callier, Anne-Claude,Quiclet-Sire, Beatrice,Zard, Samir Z.
p. 6109 - 6112
(2007/10/02)
Optical and Neutron Inelastic Scattering Study of 2-Methylnorbornanes
We have measured the infrared, Raman, and neutron vibrational spectra of the 2-methylnorbornanes with a CH3 or CD3 methyl group in the exo or endo position.A normal coordinate analysis has been carried out.The torsional modes of the methyl group are assigned at 240 and 235 cm-1 for the hydrogenated exo and endo isomers, respectively.The corresponding barrier is 15.2 +/- 0.2 kJ mol-1.The calculated neutron intensities are in good agreement with the experimental data.The frequencies are used for the determination of the thermodynamic contribution to the standard free energy difference.