Pd/TEMPO Double-mediatory Electrooxidative Wacker-type Cyclizations

Reconciling the stereochemical course of nucleopalladation with the development of enantioselective wacker-type cyclizations.

Palladium-catalyzed oxidative wacker cyclizations in nonpolar organic solvents with molecular oxygen: a stepping stone to asymmetric aerobic cyclizations.

Catalytic asymmetric oxidation-chemistry involving heteroatom transfer from a reagent to a substrate is perhaps unparalleled in synthetic utility for the construction of enantioenriched materials.[1] Conversely, there is a significant deficiency of asymmetric two-electron oxidations that do not involve heteroatom transfer. Some potentially valuable reactions of this type include the oxidation o...

Synthesis of vicinal aminoalcohols by stereoselective aza-Wacker cyclizations: access to (-)-acosamine by redox relay.

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...

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...