Premium
Rh II ‐Catalyzed Reactions of Diazocarbonyl Compounds with Dicarboximides
Author(s) -
Nikolaev Vsevolod V.,
Heimgartner Heinz,
Linden Anthony,
Krylov Ivan S.,
Nikolaev Valerij A.
Publication year - 2006
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200600396
Subject(s) - chemistry , intramolecular force , diazo , carbene , moiety , phthalimide , medicinal chemistry , catalysis , decarbonylation , photochemistry , stereochemistry , organic chemistry
The reaction of Rh II –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 O ‐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)