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Updated: Oct 3, 2026

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Cyclopropanation with Diazomethane and Bis(oxazoline)palladium(II) Complexes
Scott E. Denmark1, Robert A. Stavenger, Anne-Marie Faucher
1Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801.
Abstract:
Studies toward the development of an enantioselective diazomethane-based cyclopropanation reagent derived from bis(oxazoline)palladium(II) complexes are reported. Several simple palladium chelates, 2 and 7, in addition to the novel carbon-bound complexes 15 were synthesized and evaluated in the cyclopropanation of various electron-deficient olefins. The X-ray crystal structure of aryl-bis(oxazoline)palladium complex 15c is described. Although all catalysts efficiently affected cyclopropanation, all products were racemic. An intriguing relationship between substitution on the oxazoline ring, particularly the commonly-derivatized 4-position, and catalyst efficiency was discovered. The results are rationalized by either partial or complete bis(oxazoline) decomplexation during the course of the reaction.
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Preparation of Epoxides
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...