Media type: E-Article Title: RhII‐Catalyzed Reactions of Diazocarbonyl Compounds with Dicarboximides Contributor: Nikolaev, Vsevolod V.; Heimgartner, Heinz; Linden, Anthony; Krylov, Ivan S.; Nikolaev, Valerij A. imprint: Wiley, 2006 Published in: European Journal of Organic Chemistry Language: English DOI: 10.1002/ejoc.200600396 ISSN: 1434-193X; 1099-0690 Keywords: Organic Chemistry ; Physical and Theoretical Chemistry Origination: Footnote: Description: <jats:title>Abstract</jats:title><jats:p>The reaction of Rh<jats:sup>II</jats:sup>–oxocarbenoids derived from acyclic diazocarbonyl compounds with phthalimide and succinimide proceeds chemoselectively at the oxygen atom of the imidic carbonyl group, giving rise to the intermediate formation of carbonyl ylides. Intramolecular stabilization of these highly reactive species occurs in three different ways, and is controlled by the structure of the 2‐oxocarbenoids. Carbonyl ylides from diazo esters mainly experience a [1,4]‐hydrogen shift, and in this case, the corresponding <jats:italic>O</jats:italic>‐alkylimidates are formed as the final products. These ylides may also be stabilized by 1,3‐dipolar electrocyclization with intermediate formation of an oxirane. Carbonyl ylides with an acyl group in the carbene moiety undergo an intramolecular 1,5‐dipolar electrocyclization to produce 1,3‐dioxole derivatives. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)</jats:p>