Aldehyde‐Selective Wacker‐Type Oxidation of Unbiased Alkenes Enabled by a Nitrite Co‐Catalyst

Abstract

Breaking the rules: Reversal of the high Markovnikov selectivity of Wacker-type oxidations was accomplished using a nitrite co-catalyst. Unbiased aliphatic alkenes can be oxidized with high yield and aldehyde selectivity, and several functional groups are tolerated. ¹⁸O-labeling experiments indicate that the aldehydic O atom is derived from the nitrit

Catalytic Isohypsic‐Redox Sequences for the Rapid Generation of Csp3‐Containing Heterocycles

“…We then turned our attention to the possible aldehyde‐selective Wacker‐type alkene oxidation developed by Feringa and Grubbs et al . Using silver nitrite and copper(II) chloride as co‐catalysts resulted in formation of the expected aldehyde as the major product in a modest overall yield consistent with the yields reported for these two processes in isolation ( 5 to 7 ) . Interestingly, the presence of a nitrile ligand (as used in earlier work by Feringa and Grubbs et al.)…”

Palladium‐Catalyzed anti‐Markovnikov Oxidation of Terminal Alkenes

“…[22] The catalyst system comprised [PdCl 2 (PhCN) 2 ], CuCl 2 , and AgNO 2 in tert-butanol/MeNO 2 at 20-25 8C. An aldehyde/ketone ratio of 4:1 was obtained in the oxidation of 1-dodecene, however the yield of the aldehyde was reduced by the partly competitive formation of olefin isomerization products.…”

Wacker Oxidation of Terminal Alkenes Over ZrO2‐Supported Pd Nanoparticles Under Acid‐ and Cocatalyst‐Free Conditions

“…[1] Moreover,t he general requirement of an acidic environment or excess chloride ions not only causes reactor corrosion but also lowersp roduct selectivity by generatingc hlorinated byproducts. [1,3] To overcome these limitations, many efforts have focused on refining the oxidants, [4] solvents, [5] and additives [6] andr eplacing metal cocatalysts with organic ligands. [7] However,m osto ft heset echniquess imultaneously create new issues;t he removal of associated ligandsi so ften difficult, and the complexity of these catalytic systemsm ay preclude their application on al arge scale.…”