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  • Title: Stereochemistry of intermolecular oxypalladation: Pd(II)-catalyzed 1,3-chirality transfer reaction of chiral allylic alcohol with methanol.
    Author: Vikhe YS, Hande SM, Kawai N, Uenishi J.
    Journal: J Org Chem; 2009 Aug 07; 74(15):5174-80. PubMed ID: 19719250.
    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.
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