title: Stereochemistry of intermolecular oxypalladation: Pd(II)-catalyzed 1,3-chirality transfer reaction of chiral allylic alcohol with methanol.
abstract: The intermolecular oxypalladation of chiral nonracemic allylic alcohols (S)-1, (R)-1, and (R)-3 in methanol gave chiral nonracemic methyl allyl ethers (S)-2 and/or (R)-2 with excellent selectivity. The reaction induced the 1,3-chirality transfer to give syn-S(N)2' product exclusively through syn oxypalladation. On the other hand, the anti-S(N)2' product was produced in 20-33% in THF, toluene, and CH2Cl2 and predominantly in CH3CN. The pi-olefin-Pd complexes I and II are proposed as important intermediates to explain the syn- and anti-oxypalladation pathways. The byproduct 9 was formed through the second syn-oxypalladation from the methyl allyl ether 2, though the rate of this second reaction was far slower than that of allylic alcohol.
authors.affiliation: Kyoto Pharmaceutical University, Misasagi, Yamashina, Kyoto 607-8412, Japan.
authors.forename: Yogesh S
authors.initials: YS
authors.lastname: Vikhe
authors.forename: Sudhir M
authors.initials: SM
authors.lastname: Hande
authors.forename: Nobuyuki
authors.initials: N
authors.lastname: Kawai
authors.forename: Jun'ichi
authors.initials: J
authors.lastname: Uenishi
mesh_terms: D002384:Catalysis; D004987:Ethers / Q000138:chemical synthesis / Q000737:chemistry*; D000432:Methanol / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D020005:Propanols / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D004987:Ethers; D009942:Organometallic Compounds; D020005:Propanols; C006463:allyl alcohol; D010165:Palladium; D000432:Methanol