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A method for the regioselective 1,2‐arylboration of 1,3‐butadiene, a feedstock chemical, is reported. The reactions result in the formation of products that can be easily elaborated to other structures. The mechanistic details of this process are also discussed. [ABSTRACT FROM AUTHOR]

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 β‐hydride elimination/reinsertion cascade. Enantioselective variants of both processes are presented as well as mechanistic investigations. Keep your options open: Methods were developed for both the 1,2‐ and 1,1‐arylboration of α‐alkyl alkenyl arenes, including enantioselective variants. The formation of quaternary centers by 1,2‐arylboration occurred through a rare cross‐coupling of a tertiary organometallic complex (see scheme). 1,1‐Arylboration was enabled by catalyst optimization and occurred through a β‐hydride elimination/reinsertion cascade. [ABSTRACT FROM AUTHOR]

A method for the diastereoselective carboboration of 1,2-disubstituted styrenes with aryl/vinyl bromides and (Bpin)2 is reported. High diastereoselectivities and yields are observed for the formation of either diastereomer of the product from a single alkene isomer. These reactions provide access to a diverse range of structures from simple starting materials. [ABSTRACT FROM AUTHOR]

Copper-catalyzed Suzuki-Miyaura-type cross-coupling and carboboration processes are reported. The cross-couplings function well with a variety of substituted aryl iodides and aryl boronic esters and allows for orthogonal reactivity compared to palladium-catalyzed processes. The carboboration method includes both alkynes and allenes and provides access to highly substituted and stereodefined vinyl boronic esters. The alkyne carboboration method is highlighted in the simple one-pot synthesis of Tamoxifen. [ABSTRACT FROM AUTHOR]