title: Silicon-directed rhenium-catalyzed allylic carbaminations and oxidative fragmentations of γ-silyl allylic alcohols.
abstract: A highly regioselective allylic substitution of β-silyl allylic alcohols has been achieved that provides the branched isomer as a single product. This high level of regiocontrol is achieved through the use of a vinyl silane group that can perform a Hiyama coupling providing 1,3-disubstituted allylic amines. An unusual oxidative fragmentation product was also observed at elevated temperature that appears to proceed by a Fleming-Tamao-type oxidation-elimination pathway.
authors.affiliation: School of Chemistry and Chemical Engineering, Queen's University Belfast, Belfast. BT9 5AG (Northern Ireland), Fax: (+44) 28-9097-6524.
authors.forename: Sanjay W
authors.initials: SW
authors.lastname: Chavhan
authors.forename: Matthew J
authors.initials: MJ
authors.lastname: Cook
mesh_terms: D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D000586:Amination; D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D007536:Isomerism; D010084:Oxidation-Reduction; D020005:Propanols / Q000138:chemical synthesis / Q000737:chemistry*; D012211:Rhenium / Q000737:chemistry*; D012821:Silanes / Q000138:chemical synthesis / Q000737:chemistry; D012825:Silicon / Q000737:chemistry*
chemical_list: D000498:Allyl Compounds; D000588:Amines; D020005:Propanols; D012821:Silanes; C006463:allyl alcohol; D012211:Rhenium; D012825:Silicon
keywords: Hiyama coupling; allylic substitution; carbamination; rhenium; silicon