{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Sang HL"],"funding":["National University of Singapore"],"pagination":["973-978"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC5873224"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["9(4)"],"pubmed_abstract":["We report the first stereoconvergent Markovnikov 1,2-hydrosilylation of conjugated dienes using catalysts generated from bench-stable Co(acac)<sub>2</sub> and phosphine ligands. A wide range of <i>E</i>/<i>Z</i>-dienes underwent this Markovnikov 1,2-hydrosilylation in a stereoconvergent manner, affording (<i>E</i>)-allylsilanes in high isolated yields with high stereoselectivities (<i>E</i>/<i>Z</i> = >99 : 1) and high regioselectivities (<i>b</i>/<i>l</i> up to > 99 : 1). Mechanistic studies revealed that this stereoconvergence stems from a σ-π-σ isomerization of an allylcobalt species generated by the 1,4-hydrometalation of <i>Z</i>-dienes. In addition, a cobalt catalyst that can only catalyze the hydrosilylation of the <i>E</i>-isomer of an (<i>E</i>/<i>Z</i>)-diene was identified, whic"],"journal":["Chemical science"],"pubmed_title":["Cobalt-catalyzed regioselective stereoconvergent Markovnikov 1,2-hydrosilylation of conjugated dienes."],"pmcid":["PMC5873224"],"funding_grant_id":["R-143-000-614-133","R-143-000-630-133"],"pubmed_authors":["Ge S","Sang HL","Yu S"],"additional_accession":[]},"is_claimable":false,"name":"Cobalt-catalyzed regioselective stereoconvergent Markovnikov 1,2-hydrosilylation of conjugated dienes.","description":"We report the first stereoconvergent Markovnikov 1,2-hydrosilylation of conjugated dienes using catalysts generated from bench-stable Co(acac)<sub>2</sub> and phosphine ligands. A wide range of <i>E</i>/<i>Z</i>-dienes underwent this Markovnikov 1,2-hydrosilylation in a stereoconvergent manner, affording (<i>E</i>)-allylsilanes in high isolated yields with high stereoselectivities (<i>E</i>/<i>Z</i> = >99 : 1) and high regioselectivities (<i>b</i>/<i>l</i> up to > 99 : 1). Mechanistic studies revealed that this stereoconvergence stems from a σ-π-σ isomerization of an allylcobalt species generated by the 1,4-hydrometalation of <i>Z</i>-dienes. In addition, a cobalt catalyst that can only catalyze the hydrosilylation of the <i>E</i>-isomer of an (<i>E</i>/<i>Z</i>)-diene was identified, whic","dates":{"release":"2018-01-01T00:00:00Z","publication":"2018 Jan","modification":"2026-05-05T23:34:41.293Z","creation":"2019-03-26T23:25:57Z"},"accession":"S-EPMC5873224","cross_references":{"pubmed":["29629163"],"doi":["10.1039/c7sc04002d"]}}