(Z)-Selective Hydrosilylation and Hydroboration of Terminal Alkynes Enabled by Ruthenium Complexes with an N-Heterocyclic Carbene Ligand.

Metal-catalyzed trans-1,2-hydrosilylations and hydroborations of terminal alkynes that generate synthetically valuable (Z)-alkenylsilanes and (Z)-alkenylboranes remain challenging due to the (E)-selective nature of the reactions and the formation of the thermodynamically unfavorable (Z)-isomer. The development of new, efficient catalytic systems for the (Z)-selective hydrosilylation and hydroboration of terminal alkynes is thus highly desirable from a fundamental perspective as it would deepen our understanding of the metal-catalyzed (Z)-selective hydrosilylation and hydroboration of terminal alkynes. This personal account describes our research for developing a ruthenium complex that can efficiently catalyze the hydrosilylation and hydroboration of terminal alkynes, and for exploring the factors controlling (Z)-selectivity of the reactions. Our effort into the activation of B-protected boronic acids, R-B(dan) (dan=naphthalene-1,8-diaminato), that was believed not to participate in Suzuki-Miyaura cross-coupling, is also discussed.

Mild and Practical Indole C2 Allylation by Allylboration of in situ Generated 3-Chloroindolenines.

C2 allylation of indole derivatives is a challenging but important transformation given the biological relevance of the products. Herein we report a selective C2 allylation strategy that proceeds via allylboration of in situ-generated 3-chloroindolenines. The reaction is mild, practical, and compatible with a wide range of C3-substituted indoles. As allylboronates are readily accessible from commercial precursors, various substituted allyl moieties can be introduced using the same protocol. To showcase the utility of this method we applied it to the synthesis of the natural product, tryprostatin B.

Synthesis and Reactivity of α-Cumyl Bromodifluoromethanesulfenate: Application to the Radiosynthesis of [18 F]ArylSCF3.

A highly reactive electrophilic bromodifluoromethylthiolating reagent, α-cumyl bromodifluoro-methanesulfenate 1, was prepared to allow for direct bromodifluoromethylthiolation of aryl boron reagents. This coupling reaction takes place under copper catalysis, and affords a large range of bromodifluoromethylthiolated arenes. These compounds are amenable to various transformations including halogen exchange with [18 F]KF/K222 , a process giving access to [18 F]arylSCF3 in two steps from the corresponding aryl boronic pinacol esters.

Copper-Mediated Nucleophilic Radiobromination of Aryl Boron Precursors: Convenient Preparation of a Radiobrominated PARP-1 Inhibitor.

The copper-mediated nucleophilic radiobromination of aryl boron precursors with a radiobromide ion is a novel radiolabeling method that is efficient and robust. High radiochemical conversion (RCC) was observed using a variety of solvents, temperatures and catalysts. The reaction is also clean and is feasible for purification to obtain high chemical and radiochemical purity. This method provides a very useful route for the preparation of radiobrominated pharmaceuticals, including a radiobromine labeled PARP-1 inhibitor, and it is a valuable addition to the family of copper-mediated radiolabeling processes.