Pd‐Mediated Reactions of Epoxides

Abstract

This review highlights the different reactions of epoxides induced by stoichiometric or catalytic amounts of palladium, except for hydrogenolysis procedures and reactions involving additions to α,β‐unsaturated epoxides. The proposed mechanisms are described, with some personal observations in some cases.

The Reims Journey Towards Discovery and Understanding of Pd-Catalyzed Oxidations

“…However, the strong acceleration of the palladium-catalyzed reaction of 32 (Equation (19)) indicates some participation of Pd(OCOCF 3 ) 2 /L H in the process [80]. In fact, epoxides are very sensitive to Pd catalysis [84]. Complementary mechanistic experiments and ESI-MS studies supported the proposed reaction pathway [85].…”

Practical Direct α‐Arylation of Cyclopentanones by Palladium/Enamine Cooperative Catalysis

“…2) The kinetics of forming the enamine and X‐Pd II ‐aryl species need to match each other. Otherwise, known side reactions, such as enamine‐aldol, ketone dehydrogenation, and aryl dimerization can compete. Hence, to test the feasibility of this strategy, cyclopentanone and PhBr were employed as model substrates.…”

Oxidation and Reduction

“…MeCN could also react as a nucleophile being hydrolysed in the presence of water to give intermediate (30). The reductive elimination of (30) formed the new C(sp 3 )-OH, C(sp 3 )-OR, and C(sp 3 )-N bonds (31). With PhI(OAc) 2 , the direct reductive elimination in (29) afforded the observed aminoacetoxylation products.…”

“…30 Plausible mechanisms have been provided in most cases for Pd-catalysed oxidation of alkynes, for which reactivity, selectivity, and products depended on the substitution of the triple bond; 1,2-diarylethynes were the most reactive. 31 A review focuses on the discovery and development of 2-iodoxybenzenesulfonic acid and related hypervalent iodine compounds that are chemoselective oxidants and environmentally benign. It covers advances in hypervalent iodine-catalysed alcohol oxidations and related transformations.…”