Dual Ruthenium-Catalyzed Alkene Isomerization-Hydrogen Auto-Transfer Unlocks Skipped Dienes as Pronucleophiles for Enantioselective Alcohol C-H Allylation.

ABSTRACT: The first use of 1,4-pentadiene and 1,5-hexadiene as allylmetal pronucleophiles in regio-, anti-diastereo-, and enantioselective carbonyl addition from alcohol proelectrophiles is described. As corroborated by deuterium labeling experiments, primary alcohol dehydrogenation delivers a ruthenium hydride that affects alkene isomerization to furnish a conjugated diene, followed by transfer hydrogenative carbonyl addition. Hydrometalation appears to be assisted by the formation of a fluxional olefin-chelated homoallylic alkylruthenium complex II, which exists in equilibrium with its pentacoordinate η¹ form to enable β-hydride elimination. This effect confers remarkable chemoselectivity: while 1,4-pentadiene and 1,5-hexadiene are competent pronucleophiles, higher 1,n<

SUBMITTER: Dubey ZJ 

PROVIDER: S-EPMC10551046 | biostudies-literature | 2023 Apr

REPOSITORIES: biostudies-literature