Sendra Jana, Manzano Ruben, Reyes Efraim, Vicario Jose L, Fernández Elena
Department Química Física i Inorgànica, University Rovira i Virgili, C/ Marcel⋅lí Domingo s/n, Spain.
Department of Organic Chemistry II, University of the Basque Country (UPV/EHU), P.O. Box 644, 48080, Bilbao, Spain.
Angew Chem Int Ed Engl. 2020 Jan 27;59(5):2100-2104. doi: 10.1002/anie.201913438. Epub 2019 Dec 18.
Medium-sized carbocycles containing an α,β-unsaturated ketone moiety as Michael acceptor site and a ketone moiety as internal electrophilic site are ideal substrates to conduct Cu(I)-catalyzed conjugated borylation followed by electrophilic intramolecular trapping that results into a pioneer transannular borylative ring closing reaction. The relative configuration of three adjacent stereocenters is controlled, giving access to a single diastereoisomer for a wide range of substrates tested. Moreover, when a chiral ligand is incorporated, the reaction provides enantioenriched polycyclic products with up to 99 % ee.
含有作为迈克尔受体位点的α,β-不饱和酮部分和作为分子内亲电位点的酮部分的中等大小碳环是进行铜（I）催化的共轭硼化反应，随后进行亲电分子内捕获从而实现首例跨环硼化闭环反应的理想底物。三个相邻立体中心的相对构型得到控制，对于所测试的多种底物都能得到单一非对映异构体。此外，当引入手性配体时，该反应能提供对映体富集的多环产物，对映体过量高达99%。
