Electrode-mediated Wacker oxidation of cyclic and internal olefins

Unraveling the Wacker oxidation mechanisms.

The Wacker processsolefin oxidation via a Pd(II)Cl2 catalyst and an air-recyclable CuCl2 co-oxidant (Scheme 1)swas one of the most important industrial breakthroughs in the fabrication of organic chemicals, and is widely regarded as one of the quintessential organometallic processes.1 Besides its industrial importance, the Wacker process and its analogues are continually used in fields relating...

Efficient and highly aldehyde selective Wacker oxidation.

A method for efficient and aldehyde-selective Wacker oxidation of aryl-substituted olefins using PdCl(2)(MeCN)(2), 1,4-benzoquinone, and t-BuOH in air is described. Up to a 96% yield of aldehyde can be obtained, and up to 99% selectivity can be achieved with styrene-related substrates.

Regioselective Wacker oxidation of internal alkenes: rapid access to functionalized ketones facilitated by cross-metathesis.

Terminal olefins to linear α,β-unsaturated ketones: Pd(II)/hypervalent iodine co-catalyzed Wacker oxidation-dehydrogenation.

Development of a mild (35 °C, no Brønsted acids) tandem Wacker oxidation-dehydrogenation of terminal olefins was accomplished using palladium(II) and hypervalent iodine co-catalysis. The reaction affords linear aryl and alkyl α,β-unsaturated ketones directly from readily available terminal olefins in good yields (average 75% per step) with excellent functional group tolerance and chemo- and ste...

Catalyst-controlled Wacker-type oxidation: facile access to functionalized aldehydes.

The aldehyde-selective oxidation of alkenes bearing diverse oxygen groups in the allylic and homoallylic position was accomplished with a nitrite-modified Wacker oxidation. Readily available oxygenated alkenes were oxidized in up to 88% aldehyde yield and as high as 97% aldehyde selectivity. The aldehyde-selective oxidation enabled the rapid, enantioselective synthesis of an important pharmaceu...