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Unusual reactions of diazocarbonyl compounds with ?,?-unsaturated ?-amino esters: Rh(II)-catalyzed Wolff rearrangement and oxidative cleavage of N-H-insertion products.

ABSTRACT: Rh(II)-?atalyzed reactions of aroyldiazomethanes, diazoketoesters and diazodiketones with ?,?-unsaturated ?-aminoesters, in contrast to reactions of diazomalonates and other diazoesters, give rise to the Wolff rearrangement and/or oxidative cleavage of the initially formed N-H-insertion products. These oxidation processes are mediated by Rh(II) catalysts possessing perfluorinated ligands. The formation of pyrrolidine structures, characteristic for catalytic reactions of diazoesters, was not observed in these processes at all.

SUBMITTER: Nikolaev VA

PROVIDER: S-EPMC5082446 | biostudies-literature | 2016

REPOSITORIES: biostudies-literature

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Unusual reactions of diazocarbonyl compounds with α,β-unsaturated δ-amino esters: Rh(II)-catalyzed Wolff rearrangement and oxidative cleavage of N-H-insertion products.

Nikolaev Valerij A VA Medvedev Jury J JJ Galkina Olesia S OS Azarova Ksenia V KV Schneider Christoph C

Beilstein journal of organic chemistry 20160825

Rh(II)-сatalyzed reactions of aroyldiazomethanes, diazoketoesters and diazodiketones with α,β-unsaturated δ-aminoesters, in contrast to reactions of diazomalonates and other diazoesters, give rise to the Wolff rearrangement and/or oxidative cleavage of the initially formed N-H-insertion products. These oxidation processes are mediated by Rh(II) catalysts possessing perfluorinated ligands. The formation of pyrrolidine structures, characteristic for catalytic reactions of diazoesters, was not obse ...[more]

PMID: 27829897

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