Regio- and enantioselective iridium-catalyzed intermolecular allylic etherification of achiral allylic carbonates with phenoxides.
An enantioselective and regioselective iridium-catalyzed allylic etherification is described. The reaction of sodium and lithium aryloxides with achiral (E)-cinnamyl and terminal aliphatic allylic electrophiles in the presence of 2 mol % of an iridium-phosphoramidite complex provides chiral allylic aryl ethers in high yields and excellent levels of regio- and enantioselectivity. Lithium aryloxides containing a single substituent at an ortho, meta, or para position as well as sterically hindered phenoxides were tolerated. Reactions in THF displayed the most suitable balance of rate, regio-, and enantioselectivity. High ee's were also observed for the products from the reaction of alkyl (E)-allylic carbonates.
López
Fernando
F
Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
Ohmura
Toshimichi
T
Hartwig
John F
JF
D000498:Allyl Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D002254:Carbonates / Q000737:chemistry*; D002384:Catalysis; D004987:Ethers / Q000138:chemical synthesis*; D007495:Iridium / Q000737:chemistry*; D010087:Oxides / Q000737:chemistry*; D013237:Stereoisomerism
D000498:Allyl Compounds; D002254:Carbonates; D004987:Ethers; D010087:Oxides; D007495:Iridium