Modular Synthesis of a Versatile Double-Allylation Reagent for Complex Diol Synthesis.

Double-allylation reagents allow for the construction of highly complex molecules in an expedient fashion. We have developed an efficient, modular, and enantioselective approach towards accessing novel variants of these reagents through Cu/Pd-catalyzed alkenylboration of alkenylboron derivatives. Importantly, we demonstrate novel use of an allylBdan reagent directly in a stereocontrolled allylation without initial deprotection to the boronic ester. These allylation products are employed in a second intermolecular allylation to access complex diol motifs, which has yet to be shown with these types of double-allylation reagents. Overall, the modularity of this approach and the ease in which complex structural motifs can be accessed in a rapid manner signify the importance and utility of this method.

Catalyst-Controlled 1,2- and 1,1-Arylboration of α-Alkyl Alkenyl Arenes.

Two methods are reported for the 1,2- and 1,1-arylboration of α-methyl vinyl arenes. In the case of 1,2-arylboration, the formation of a quaternary center occurred through a rare cross-coupling reaction of a tertiary organometallic complex. 1,1-Arylboration was enabled by catalyst optimization and occurred through a ß-hydride elimination/reinsertion cascade. Enantioselective variants of both processes are presented as well as mechanistic investigations.

Cooperative Pd/Cu Catalysis for Alkene Arylboration: Opportunities for Divergent Reactivity.

A preeminent challenge in alkene difunctionalization is the control of regio-, diastereo-, and enantioselectivity. In this Perspective, a Pd/Cu-cooperative catalytic system for alkene arylboration is highlighted that allows for the controlled introduction of substituents. In particular, examples that allowed for divergent reactivity from a single substrate based on the tuning of catalysts and reaction conditions are emphasized.

Rhodium-Catalyzed Interconversion of Quinolinyl Ketones with Boronic Acids via C-C Bond Activation.

A rhodium-catalyzed cross-coupling of aryl and aliphatic quinolinyl ketones with boronic acids has been developed. Proceeding via quinoline-directed carbon-carbon σ bond activation, the transformation demonstrates tolerance of a range of functional groups on both the ketone and aryl boronic acid substrates, providing good to excellent yields of the new ketones, particularly those containing electron-withdrawing substituents. Catalyst reactivity is dependent on quinolinyl ketone substrates, with alkyl ketones requiring Rh(PPh3)3Cl instead of the more reactive [Rh(C2H4)2Cl]2. With the use of K2CO3 as an additive, methyl boronic acid is also a competent substrate, giving rise to an unprecedented methylation technique.