Oxidation of Olefins to Carbonyl Compounds: Modern View of the Classical Reaction
- PDF / 3,554,170 Bytes
- 58 Pages / 612 x 792 pts (letter) Page_size
- 40 Downloads / 212 Views
cated to Academician I. I. Moiseev, one of the founders of modern metal complex catalysis, on the occasion of his 90th birthday and 60th anniversary of the discovery of olefin oxidation
Oxidation of Olefins to Carbonyl Compounds: Modern View of the Classical Reaction O. N. Temkin* MIREA–Russian Technological University (Lomonosov Institute of Fine Chemical Technologies), Moscow, 119571 Russia *e-mail: [email protected] Received November 18, 2019; revised March 27, 2020; accepted March 27, 2020
Abstract—The results of 60 years' research into the mechanisms of olefin oxidation catalyzed by palladium complexes (Wacker oxidation) are analyzed. The concepts of the mechanisms of related oxidative carboxylations (Moiseev reaction) and alkoxylations are discussed. This review considers the regularities of processes in aqueous organic solvents; the problems of regio- and stereoselectivity of reactions; and the role of co-catalysts, oxidants, and ligands, including asymmetric catalysis. The effect of transition from anionic (or neutral) to cationic palladium chloride complexes in water or aqueous organic media on the mechanism of olefin oxidation is discussed in detail. Keywords: oxidation, olefins, ketones, aldehydes, vinyl esters, anionic and cationic palladium complexes, kinetics, mechanism, regioselectivity DOI: 10.1134/S0023158420050122
CONTENTS 1. Introduction 2. History of the discovery of olefin oxidation to carbonyl compounds 3. Mechanisms of olefin oxidation in solutions of palladium(II) chloride complexes 3.1. Nucleophilic exchange in vinyl and allyl compounds and olefin oxidation in acetic acid and methanol Abbreviations: AA, acetaldehyde; anti-M, against Markovnikov rule; AAlc, allyl alcohols; APh, acetophenone; HV, hydrovinylation; HP, hydroxypalladation; HPA, heteropolyacid; DMA, acetaldehyde dimethylacetal; DEA, acetaldehyde diethylacetal; IL, ionic liquid; KIE, kinetic isotope effect; M, according to Markovnikov rule; MCI, metal-carbenium ion; PFCSs, polyfunctional catalytic systems; RS, regioselectivity; XRD, X-ray diffraction; PhI, phthalimide; ChH, chlorohydrin; CHex, cyclohexene; ECH, ethylene chlorohydrin; AIMD, ab initio molecular dynamics; AN, acetonitrile; BQ, p-benzoquinone; COD, cyclooctadiene-1,5; DFT, density functional theory; DMA, dimethylacetamide; DME, 1,2-dimethoxyethane; DMF, dimethylformamide; DMP, Dess–Martin periodinane; DMSO, dimethyl sulfoxide, NMP, N-methylpyrrolidone; Ox, oxidant; PcFe, iron phthalocyaninate complex; Q, quinone; THF, tetrahydrofuran; TMEDA, tetramethylethylenediamine; TOF, turnover frequency.
3.2. Stereochemistry of hydroxy- and alkoxypalladations of olefins 3.3. Oxidation and isomerization of allyl alcohols 3.4. Isomerization and oxidation of chiral allyl alcohols 3.5. Mechanisms of transformation of σ-organopalladium intermediates 3.6. Theoretical studies of the mechanism of Wacker oxidation 4. Olefin oxidation in binary aqueous organic solvents involving various oxidants and ligands 4.1. Various oxidants and co-catalysts 4.2. Hydrogen peroxide and ROOH: Stoichi
Data Loading...
