title: Iridium-catalyzed hydrocarboxylation of 1,1-dimethylallene: byproduct-free reverse prenylation of carboxylic acids.
abstract: Exposure of carboxylic acids 1a-12a to commercially available 1,1-dimethylallene in the presence of substoichiometric quantities of an iridium catalyst prepared in situ from [Ir(cod)Cl]2 and BIPHEP provides the corresponding 1,1-dimethylallyl (reverse prenyl) esters 1b-12b in 74-92% isolated yield. This protocol represents the first branch-regioselective allene hydrocarboxylation. Stoichiometric byproducts are not generated in this process and protecting groups are not required for alcohols, phenols, and indolic amines.
authors.affiliation: University of Texas at Austin, Department of Chemistry and Biochemistry, Austin, Texas 78712, USA.
authors.forename: In Su
authors.initials: IS
authors.lastname: Kim
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Krische
mesh_terms: D000466:Alkadienes / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D004952:Esters; D007495:Iridium / Q000737:chemistry*; D015394:Molecular Structure; D054876:Prenylation; D013237:Stereoisomerism
chemical_list: D000466:Alkadienes; D002264:Carboxylic Acids; D004952:Esters; D007495:Iridium; C025947:propadiene