title: Catalytic enantioselective Grignard Nozaki-Hiyama methallylation from the alcohol oxidation level: chloride compensates for π-complex instability.
abstract: Methallyl chloride serves as an efficient allyl donor in highly enantioselective Grignard Nozaki-Hiyama methallylations from the alcohol or aldehyde oxidation level via iridium catalyzed transfer hydrogenation. Under identical conditions, methallyl acetate does not react efficiently. Double methallylation of 1,3-propanediol provides the C(2)-symmetric adduct as a single enantiomer, as determined by HPLC analysis.
authors.affiliation: Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, TX 78712, USA.
authors.forename: Abbas
authors.initials: A
authors.lastname: Hassan
authors.forename: Ian A
authors.initials: IA
authors.lastname: Townsend
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Krische
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D000447:Aldehydes / Q000737:chemistry; D002384:Catalysis; D002712:Chlorides / Q000737:chemistry*; D002851:Chromatography, High Pressure Liquid; D006865:Hydrogenation; D007495:Iridium / Q000737:chemistry; D010084:Oxidation-Reduction; D011409:Propylene Glycols / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000438:Alcohols; D000447:Aldehydes; D002712:Chlorides; D011409:Propylene Glycols; D007495:Iridium; C041787:1,3-propanediol