Stereochemistry of intermolecular oxypalladation: Pd(II)-catalyzed 1,3-chirality transfer reaction of chiral allylic alcohol with methanol.
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.
Vikhe
Yogesh S
YS
Kyoto Pharmaceutical University, Misasagi, Yamashina, Kyoto 607-8412, Japan.
Hande
Sudhir M
SM
Kawai
Nobuyuki
N
Uenishi
Jun'ichi
J
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
D004987:Ethers; D009942:Organometallic Compounds; D020005:Propanols; C006463:allyl alcohol; D010165:Palladium; D000432:Methanol