Palladium-Catalyzed/Titanium-Promoted Csp3–Csp3 Coupling of Two Alcohols: Generation of an All-Carbon Quaternary Center

Naturally abundant and inexpensive alcohols represent appealing and suitable Csp3 coupling partners in transition metal-catalyzed cross-coupling reactions. A palladium-catalyzed/titanium-promoted Csp3-Csp3 cross coupling between two distinct unprotected alcohols has been accomplished. The reaction features a Pd-catalyzed β-H elimination, enabling the reversal of the electrophilic π-allyl-Pd intermediate into a nucleophilic dienolate and the generation of an all-carbon quaternary center.