Zhang, ZheyeChen, Ming2025-10-142025-10-142024-11-191523-7060https://hdl.handle.net/10919/138179Stereo- and enantioselective syntheses of 1,2-oxaborinan-3-enes and delta-boryl-substituted homoallylic alcohols are reported. We developed a practical approach to synthesize alpha-boryl-substituted allylboronate. This reagent was utilized to generate alpha,alpha-disubstituted allylboronates, and such reagents cannot be accessed via the Pd-catalyzed alkene isomerization approach. Chiral Br & oslash;nsted-acid-catalyzed aldehyde addition with these reagents gave 1,2-oxaborinan-3-enes with excellent stereo- and enantioselectivities. Lewis-acid-catalyzed aldehyde addition also worked well, affording delta-boryl-substituted homoallylic alcohols with high stereoselectivities. The enantioselective variant of the reaction was achieved via a chiral Br & oslash;nsted-acid-catalyzed aldehyde addition and Pd-catalyzed alkene isomerization approach.application/pdfenCreative Commons Attribution 4.0 InternationalArticle - Refereedhttps://doi.org/10.1021/acs.orglett.4c037552647395614011523-7052