Metal-free cascade construction of C–C bonds by activation of inert C(sp3)–H bonds

A direct, regioselective and eco-friendly C3-nitration of quinoline N-oxides using tert-butyl nitrite as both the nitro source and oxidant has been developed. This reaction undergoes a free radical process and can be smoothly scaled up to gram scale.

Download Full-text

ChemInform Abstract: THE DECARBOXYLATION OF SOME α-ETHOXYCARBONYLOXYBENZYL CYANIDES. PART 2. ,2-DICYANO-1,2-BIS(3,4-DIMETHOXYPHENYL)ETHANE, A MINOR PRODUCT FORMED FR M 3,4-DIMETHOXY-α-ETHOXYCARBONYLOXYBENZYL CYANIDE BY A FREE-RADICAL PROCESS

Chemischer Informationsdienst ◽

10.1002/chin.198338142 ◽

1983 ◽

Vol 14 (38) ◽

Author(s):

S. S. BANSAL ◽

J. BRUCE ◽

K. M. GILLESPIE ◽

J. A. D. JEFFREYS

Keyword(s):

Free Radical ◽

Radical Process ◽

A Minor ◽

Free Radical Process

Download Full-text

Absolute rate constants for hydrocarbon autoxidation. 32. On the self-reaction of 1,1-diphenylethylperoxyl in solution

Canadian Journal of Chemistry ◽

10.1139/v82-369 ◽

1982 ◽

Vol 60 (20) ◽

pp. 2566-2572 ◽

Cited By ~ 9

Author(s):

J. A. Howard ◽

J. H. B. Chenier ◽

T. Yamada

Keyword(s):

Free Radical ◽

Rate Constants ◽

The Self ◽

Absolute Rate ◽

Radical Process ◽

First Order ◽

Hydroperoxide Decomposition ◽

Solvent Cage ◽

Induced Decomposition ◽

Free Radical Process

The major products of the self-reaction of 1,1-diphenylethylperoxyl have been determined from product studies of the autoxidation of 1,1-diphenylethane, induced decomposition of 1,1-diphenylethyl hydroperoxide, and decomposition of 2,2,3,3-tetraphenylbutane under an atmosphere of oxygen. Overall self-reaction is a complex free-radical process involving the intermediacy of 1,1-diphenylethoxyl and 1-phenyl-1-phenoxyethoxyl which undergo H-atom abstraction, β-scission and, in the case of the former radical, rearrangement. Hydroperoxide decomposition under an atmosphere of 36O2 has shown that 1,1-diphenylethylperoxyl undergoes β-scission faster than α-cumylperoxyl at 303 K in solution. The values of the rate constants for self-reaction of Ph2C(Me)O2• relative to those for tert-butylperoxyl are, however, not affected by this reaction. Furthermore they are not affected to any appreciable extent by the efficiency with which Ph2C(Me)O•, formed in nonterminating self-reactions, escape from the solvent cage. They are influenced principally by the first-order rate of decomposition of Ph2C(Me)OOOOC(Me)Ph2.

Download Full-text

Metal-free, radical 1,6-conjugated addition of cyclic ethers with para-quinone methides (p-QMs)

Organic & Biomolecular Chemistry ◽

10.1039/c9ob00127a ◽

2019 ◽

Vol 17 (12) ◽

pp. 3239-3248 ◽

Cited By ~ 11

Author(s):

Satish G. More ◽

Gurunath Suryavanshi

Keyword(s):

Free Radical ◽

Efficient Method ◽

Bond Formation ◽

Cyclic Ethers ◽

Quinone Methides ◽

Metal Free

An efficient method for metal-free C–C bond formation between p-quinone methides (p-QMs) and cyclic ethers via a radical pathway to afford substituted diarylmethanes and triarylmethanes or to effect the α-alkylation of the cyclic ethers has been developed.

Download Full-text