Sequential catalytic isomerization and allylic substitution. Conversion of racemic branched allylic carbonates to enantioenriched allylic substitution products.
A catalytic protocol for the conversion of readily accessible racemic, branched aromatic allylic esters to branched allylic amines, ethers, and alkyls has been developed. Palladium-catalyzed isomerization of branched allylic esters to terminal allylic esters, followed by sequential iridium-catalyzed allylic substitution, gave the branched allylic products in good yield with high regioisomeric and enantiomeric selectivity. Both electron-rich and electron-poor branched allylic esters gave products in >90% ee. High enantiomeric excesses were also observed for the products from the reactions of 2-thienyl acetates and dienyl carbonates.
Shekhar
Shashank
S
Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, USA.
Trantow
Brian
B
Leitner
Andreas
A
Hartwig
John F
JF
D000498:Allyl Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D002254:Carbonates / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D007495:Iridium / Q000737:chemistry; D010165:Palladium / Q000737:chemistry; D013237:Stereoisomerism
D000498:Allyl Compounds; D002254:Carbonates; D002264:Carboxylic Acids; D007495:Iridium; D010165:Palladium