Palladium(II)-Catalysed Oxidation of Alkenes

Abstract

Abstract:This review provides a summary of recent developments in the Pd(II)-catalysed oxidation of alkenes, focusing largely on reactions which lead to the formation of new carbon-oxygen or carbon-nitrogen bonds. Three classes of reaction are covered: i) Oxidation proceeding via allylic C-H bond cleavage and formation of a -allyl complex; ii) Wackertype oxidations proceeding via nucleopalladation followed by -hydride eliminations; and iii) 1,2-Difunctionalisation of alkenes proceeding via nucleopalladation followed by functionalisation of the resulting -alkylpalladium(II) intermediate. The mechanisms are discussed alongside the scope and limitations of each reaction.

Palladium‐Catalyzed anti‐Markovnikov Halosulfonamidation of Unactivated Alkene†

“…As a result of wide interest in accessing the architectural amine skeleton, including haloamine, [ 19‐23 ] the palladium‐catalyzed methodology has been devised for its synthesis due to the high efficiency and diversity. [ 24‐28 ] Mechanistically, the appropriate oxidant, which facilitates reductive elimination to generate a carbon‐halogen bond from a high‐valent intermediate, is wildly utilized in such reactions. And the primary concern in this field is site‐selective amination of alkenes.…”

Enabling synthesis in fragment-based drug discovery (FBDD): microscale high-throughput optimisation of the medicinal chemist's toolbox reactions

“…This pathway is often energetically favourable and has been exploited in many well-known transformations including, but not limited to, Mizoroki-Heck reaction, Wacker oxidation and aza-Wacker oxidation. 16 However, if unwanted β-hydride elimination pathways occur during the synthetic elaboration of fragments with unprotected aliphatic amines, undesirable catalyst reduction and concomitant oxidative decomposition of the substrate may result. 11 Commonly medicinal chemists use protecting groups to mask potentially problematic Lewis basic and acidic fragment pharmacophores and sidechains.…”

Ni‐ and Pd‐based homogeneous catalyst systems for direct oxygenation of C(sp3)‐H groups

“…Since the discovery of the catalytic Wacker process, [90] palladium compounds have acquired a privileged position at the forefront of transition metal-mediated oxidation catalysis, demonstrating the capability of conducting various types of oxidative transformations of organic compounds, [91][92][93][94][95][96][97][98] including oxidation of alkenes, [99][100][101] alcohols, [102][103][104] and oxidative aliphatic C-H functionalizations in the presence of directing groups. [105][106][107][108][109] In contrast to first-row transition metal complexes, the involvement of palladium in direct selective C(sp 3 )-H oxygenations has remained limited until recently.…”