Allylic diboronates are highly valuable reagents in organic synthesis. Existing methods predominantly yield alkyl-substituted allylic diboronates, while the incorporation of electrophilic carbonyl groups conjugated to these allylic systems remains unknown. We present a strain-release promoted cycloaddition-based strategy that enabled access to unprecedented carbonyl conjugated secondary allylic diborons. This mild base-free method also facilitated a one-pot multicomponent cycloaddition-allylboration sequence for a highly diastereoselective installation of contiguous quaternary, tertiary and secondary carbon centers on a scaffold featuring valuable β-hydroxy ester, β-vinyl ester and vinyl boronate motifs. The synthetic utility of these densely functionalized products was demonstrated through their transformation into other rare and sterically congested alkenylborons such as borylated spiro-fused β-lactones and bicyclic γ-butyrolactones. Detailed 11B NMR, deuterium labeling and mass spectrometry studies provided insights on an unexpected base-free deboronative allylic shift reaction of conjugated allylic diboronates.
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