Efficient Stereoselective Carbocyclization to cis-1,4-Disubstituted Heterocycles Enabled by Dual Pd/Electron Transfer Mediator (ETM) Catalysis

[Image: see text] An efficient Pd/ETM (ETM = electron transfer mediator)-cocatalyzed stereoselective oxidative carbocyclization of dienallenes under aerobic oxidation conditions has been developed to afford six-membered heterocycles. The use of a bifunctional cobalt complex [Co(salophen)-HQ] as hybrid ETM gave a faster aerobic oxidation than the use of separated ETMs, indicating that intramolecular electron transfer between the hydroquinone unit and the oxidized metal macrocycle occurs. In this way, a class of important cis-1,4-disubstituted six-membered heterocycles, including dihydropyran and tetrahydropyridine derivatives were obtained in high diastereoselectivity with good functional group compatibility. The experimental and computational (DFT) studies reveal that the pendent olefin does not only act as an indispensable element for the initial allene attack involving allenic C(sp(3))–H bond cleavage, but it also induces a face-selective reaction of the olefin of the allylic group, leading to a highly diastereoselective formation of the product. Finally, the deuterium kinetic isotope effects measured suggest that the initial allenic C(sp(3))–H bond cleavage is the rate-limiting step, which was supported by DFT calculations.