A key project in our group revolves around our key report of the first ever example of a Suzuki-Miyaura cross coupling reaction using chiral secondary boronic esters.[1] This reaction generates enantiomerically enriched 1,1-diaryl ethanes, which are extremely difficult to prepare by other methods. The reaction proceeds with >90% retention of configuration in all cases except one. Remarkably, the linear boronate ester does not react under these conditions.

coupling scheme

This reaction has been expanded to include allylic boronic esters and, most recently, triaryl methane derivatives, which are extremely difficult to make in enantiomerically enriched form.

TAM

Current work in this area includes understanding the differences in reactivity of the linear and branched positions, expanding this to the synthesis of pharmaceutically relevant compounds, and further investigating the enantiospecific Suzuki-Miyaura reaction mechanistically and synthetically.

 

[1]D. Imao, B.W. Glasspoole, V.S. Laberge, C.M. Crudden*, “Cross coupling reactions of chiral secondary organoboronates with retention of chirality”. Journal of the American Chemical Society, 2009, 131, 5024-5025.