title: Ruthenium hydride-promoted dienyl isomerization: access to highly substituted 1,3-dienes.
abstract: Ruthenium hydrides were found to promote the positional isomerization of 1,3-dienes into more highly substituted 1,3-dienes in a stereoconvergent manner. The reaction can be conducted in one pot starting with terminal alkynes and alkenes by triggering decomposition of the Grubbs catalyst into a ruthenium hydride, which promotes the dienyl isomerization. The presence of an alcohol additive plays a helpful role in the reaction, significantly increasing the chemical yields. Mechanistic studies are consistent with hydrometalation of the geminally substituted alkene of the 1,3-diene and transit of the ruthenium atom across the diene framework via a π-allylruthenium intermediate.
authors: Department of Chemistry, University at Buffalo, the State University of New York, Buffalo, New York 14260-3000, United States.
authors: Joseph R
authors: JR
authors: Clark
authors: Justin R
authors: JR
authors: Griffiths
authors: Steven T
authors: ST
authors: Diver
mesh_terms: D000466:Alkadienes / Q000138:chemical synthesis* / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000466:Alkadienes; D000480:Alkynes; D009942:Organometallic Compounds; D012428:Ruthenium; D006859:Hydrogen