biostudies-literatureXiang MWelch FoundationNational Institute of General Medical SciencesNIH HHSNIGMS NIH HHS8849-8854https://www.ebi.ac.uk/biostudies/studies/S-EPMC8299538biostudies-literatureUnknown143(23)The first catalytic enantioselective ruthenium-catalyzed carbonyl reductive couplings of allene pronucleophiles is described. Using an iodide-modified ruthenium-BINAP-catalyst and <i>O</i>-benzhydryl alkoxyallene <b>1a</b>, carbonyl (α-alkoxy)allylation occurs from the alcohol or aldehyde oxidation level to form enantiomerically enriched <i>syn</i>-<i>sec,tert</i>-diols. Internal chelation directs intervention of (<i>Z</i>)-σ-alkoxyallylruthenium isomers, which engage in stereospecific carbonyl addition.Journal of the American Chemical SocietyEnantioselective Ruthenium-BINAP-Catalyzed Carbonyl Reductive Coupling of Alkoxyallenes: Convergent Construction of <i>syn-sec,tert</i>-Diols via (<i>Z</i>)-σ-Allylmetal Intermediates.PMC8299538RO1-GM093905S10 OD021508R01 GM093905F-0038Brito GAKrische MJPfaffinger DEXiang MOrtiz EfalseEnantioselective Ruthenium-BINAP-Catalyzed Carbonyl Reductive Coupling of Alkoxyallenes: Convergent Construction of <i>syn-sec,tert</i>-Diols via (<i>Z</i>)-σ-Allylmetal Intermediates.The first catalytic enantioselective ruthenium-catalyzed carbonyl reductive couplings of allene pronucleophiles is described. Using an iodide-modified ruthenium-BINAP-catalyst and <i>O</i>-benzhydryl alkoxyallene <b>1a</b>, carbonyl (α-alkoxy)allylation occurs from the alcohol or aldehyde oxidation level to form enantiomerically enriched <i>syn</i>-<i>sec,tert</i>-diols. Internal chelation directs intervention of (<i>Z</i>)-σ-alkoxyallylruthenium isomers, which engage in stereospecific carbonyl addition.2021-01-01T00:00:00Z2021 Jun2025-04-04T20:16:08.781Z2025-04-04T20:16:08.781ZS-EPMC82995383406081810.1021/jacs.1c03480