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A strategy for the photosensitized cycloaddition of alkenylboronates and allylic alcohols by a temporary coordination is presented. The process allows for the synthesis of a diverse range of cyclobutylboronates. Key to development of these reactions is the temporary coordination of the allylic alcohol to the Bpin unit. This not only allows for the reaction to proceed in an intramolecular manner but also allows for high levels of stereo and regiocontrol. A key aspect of these studies is the utility of the cycloadducts in the synthesis of complex natural products artochamin J and piperarborenine B. 

A Ni-catalyzed silylacylation of alkenes is presented. The reaction combines alkenes, ClZnSiR3, and acid chlorides to provide rapid access to β-silyl ketones. Importantly, the method involves a [Ni]-SiR3 complex as a catalytic intermediate, which is rarely described for three-component alkene functionalization. Finally, the synthetic utility of the products is demonstrated, and the mechanistic details are described. 

A new strategy for the synthesis of highly versatile cyclobutylboronates via the photosensitized [2+2]‐cycloaddition of alkenylboronates and alkenes is presented. The process is mechanistically different from other processes in that energy transfer occurs with the alkenylboronate as opposed to the other alkene. This strategy allows for the synthesis of an array of diverse cyclobutylboronates. The conversion of these adducts to other compounds as well as their utility in the synthesis of melicodenine C is demonstrated.

 

A new strategy for the synthesis of highly versatile cyclobutylboronates via the photosensitized [2+2]‐cycloaddition of alkenylboronates and alkenes is presented. The process is mechanistically different from other processes in that energy transfer occurs with the alkenylboronate as opposed to the other alkene. This strategy allows for the synthesis of an array of diverse cyclobutylboronates. The conversion of these adducts to other compounds as well as their utility in the synthesis of melicodenine C is demonstrated.

 

A method for the stereoselective [4+2]‐cycloaddition of alkenylboranes and dienes is presented. This transformation was accomplished through the introduction of a new strategy that involves the use of chiral N‐protonated alkenyl oxazaborolidines as dieneophiles. The reaction leads to the formation of products that can be readily derivatized to more complex structural motifs through stereospecific transformations of the C−B bond such as oxidation and homologation. Detailed computation evaluation of the reaction has uncovered a surprising role of the counterion on stereoselectivity.

 

A method for the stereoselective [4+2]‐cycloaddition of alkenylboranes and dienes is presented. This transformation was accomplished through the introduction of a new strategy that involves the use of chiral N‐protonated alkenyl oxazaborolidines as dieneophiles. The reaction leads to the formation of products that can be readily derivatized to more complex structural motifs through stereospecific transformations of the C−B bond such as oxidation and homologation. Detailed computation evaluation of the reaction has uncovered a surprising role of the counterion on stereoselectivity.