- Cobalt catalyzed carbonylation of unactivated C(sp3)-H bonds
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A general efficient regioselective cobalt catalyzed carbonylation of unactivated C(sp3)-H bonds of aliphatic amides was demonstrated using atmospheric (1-2 atm) carbon monoxide as a C1 source. This straightforward approach provides access to α-spiral succinimide regioselectively in a good yield. Cobalt catalyzed sp3 C-H bond carbonylation is reported for the first time including the functionalization of (β)-C-H bonds of α-1°, 2°, 3° carbons and even internal (β)-C-H bonds. Our initial mechanistic investigation reveals that the C-H activation step is irreversible and will possibly be the rate determining step.
- Barsu, Nagaraju,Bolli, Shyam Kumar,Sundararaju, Basker
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- Pd(II)-catalyzed carbonylation of C(sp3)-H bonds: A new entry to 1,4-dicarbonyl compounds
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Pd(II)-catalyzed β-C(sp3)-H carbonylation of N-arylamides under CO (1 atm) has been achieved. Following amide-directed C(sp3)-H cleavage and insertion of CO into the resulting [Pd(II)-C(sp3)] bond, intramolecular C-N reductive elimination gave the corresponding succinimides, which could be readily converted to 1,4-dicarbonyl compounds. This method was found to be effective with substrates containing α-hydrogen atoms and could be applied to effect methylene C(sp3)-H carbonylation of cyclopropanes.
- Yoo, Eun Jeong,Wasa, Masayuki,Yu, Jin-Quan
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supporting information; experimental part
p. 17378 - 17380
(2011/02/24)
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- "ONE-POT" SYNTHESIS OF DISYMMETRICALLY α,α'-DISUBSTITUTED SUCCINIC ANHYDRIDES PRECURSORS
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A "one-pot" synthesis for disymmetrically α,α'-disubstituted succinic anhydrides precursors isreported in the present paper.Substituents are aryl, primary or secondary alkyl groups.This reaction represents a simple and quick method with fair yields.
- Dana, A.,Campagnole, M.,Bourgeois, M.J.,Montaudon, E.
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p. 2981 - 2988
(2007/10/03)
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- RETROVIRAL PROTEASE INHIBITORS
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Urea-containing hydroxyethylamine peptide compounds are effective as retroviral protease inhibitors, and in particular as inhibitors of HIV protease.
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- Oxidation of α-Substituted Cyclohexanols by Nitric Acid
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The influence of α-substituents on the oxidative cleavage of cyclohexanol by nitric acid in the presence of copper(II) and vanadium(V) ions has been investigated.Following the initial oxidation to give the cyclohexanone, further reaction, leading to ring opening of the ketone, requires at least one α-hydrogen.Thus 2,2,6,6-tetramethylcyclohexanol is converted to the corresponding ketone whilst 2,2,6-trimethylcyclohexanol is oxidised to a mixture of dicarboxylic acids.The mechanisms of the oxidations are discussed and enolisation is shown to be the key to oxidative cleavage.For ketones that can give two alternative enols, reaction occurs predominantly via the more stable tautomer.
- Smith, John R. Lindsay,Thomas, C. Barry,Whittaker, Mark
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p. 2191 - 2194
(2007/10/02)
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