Trisubstituted alkenyl boronic esters are valuable intermediates in organic synthesis. The direct synthesis of these reagents from simple and inexpensive alkene precursors would be very valuable for academic and industrial chemists. We have recently developed a second-generation boryl-Heck reaction for the cross-coupling of 1,1- and 1,2-disubstituted alkenes to form trisubstituted alkenyl boronic esters. Many of the products formed cannot be synthesized via traditional alkyne hydroboration or are difficult substrates for dehydrogenative borylation. This reaction proceeds with outstanding yields and excellent <i>E/Z</i> selectivities for a variety of functionalized alkenes. Mechanistic studies are consistent with a Heck-type mechanism and show that no allyl isomer is formed during the course of the reaction. The utility of this reaction has been demsostrated with an <i>in situ</i> Suzuki reaction, which allows for rapid access to stereodefined trisubstituted alkenes.

Synthesis of trisubstituted alkenyl boronic esters: A second-generation boryl-Heck reaction

254th National Meeting (2017)

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