69462-10-8Relevant academic research and scientific papers
Copper-Catalyzed Amide Radical-Directed Cyanation of Unactivated Csp3-H Bonds
Zhang, Hongwei,Zhou, Yulu,Tian, Peiyuan,Jiang, Cuiyu
supporting information, (2019/03/19)
A method for site-selective intermolecular δ/?-Csp3-H cyanation of aliphatic sulfonamides is developed using TsCN as the cyanating reagent, catalyzed by a Cu(I)/phenanthroline complex. The mild, expeditious, and modular protocol allows efficient remote Csp3-H cyanation with good functional group tolerance and high regioselectivity. Mechanistic studies indicate that the reaction might proceed through a Cu(I)-mediated N-F bond cleavage to generate an amidyl radical, 1,5-HAT, and cyano group transfer of the resulting carbon radical with TsCN.
An Iodine-Catalyzed Hofmann-L?ffler Reaction
Martínez, Claudio,Mu?iz, Kilian
supporting information, p. 8287 - 8291 (2015/07/07)
Iodine reagents have been identified as economically and ecologically benign alternatives to transition metals, although their application as molecular catalysts in challenging C-H oxidation reactions has remained elusive. An attractive iodine oxidation catalysis is now shown to promote the convenient conversion of carbon-hydrogen bonds into carbon-nitrogen bonds with unprecedented complete selectivity. The reaction proceeds by two interlocked catalytic cycles comprising a radical chain reaction, which is initiated by visible light as energy source. This unorthodox synthetic strategy for the direct oxidative amination of alkyl groups has no biosynthetic precedence and provides an efficient and straightforward access to a general class of saturated nitrogenated heterocycles.
Photochemistry of α-oxo oximes. Part 10. Photochemistry of three cyclic α-oxo oxime methyl ethers and their acyclic analogue at λ 254 nm
Buys, Theo S. V.,Cerfontain, Hans,Geenevasen, Jan A. J.,Stunnenberg, Frank
, p. 491 - 501 (2007/10/02)
The (E)- and (Z)-isomers of the 3,3,n,n-tetramethyl-2-(methoxyimino)-1-cycloalkanones (n=5 to 7) (3a-c) and their analogue (Z)-4-(methoxyimino)-2,2,5,5-tetramethyl-3-hexanone have been irridated at λ 254 nm in acetonitrile as solvent in order to study the influence of ring size on product formation.The dependence of product composition on irridation time revealed that the (E)-isomers of 3a-c undergo both E-Z isomerization and photodecomposition, whereas the (Z)-isomers undergo only Z-E isomerization.The primary step in photodecomposition is homolysis of the N-O bond.The observed products result from the various possible reactions of initially formed methoxy and cyclic iminyl radicals 17, cyanoacyl radicals 18 formed by ring opening of 17, cyanoalkyl radicals 19 formed from 18 by decarbonylation and cyclopentaniminyl radical 20b, formed by cyclization of the 5-cyano-2-hexyl radical 19b.Mechanisms for the formation of the various products are proposed and the relative importance of the various steps is discussed, also in relation to the results obtained using carbon tetrachloride as radical scavenger.Irridation of (Z)-4 at λ 254 nm leads to decomposition with formation of 2,2-dimethylpropanenitrile, methanol, isobutane and isobutene.
