Direct, intermolecular, enantioselective, iridium-catalyzed allylation of carbamates to form carbamate-protected, branched allylic amines.
The direct reaction between carbamates and achiral allylic carbonates to form branched, conveniently protected primary allylic amines with high regioselectivity and enantioselectivity is reported. This process occurs without base or with 0.5 equiv K(3)PO(4) in the presence of a metalacyclic iridium catalyst containing a labile ethylene ligand. The reactions of aryl-, heteroaryl-, and alkyl-substituted allylic carbonates with BocNH(2), FmocNH(2), CbzNH(2), TrocNH(2), TeocNH(2), and 2-oxazolidinone occur in good yields, with high selectivity for the branched isomer and high enantioselectivities (98% average ee).
Weix
Daniel J
DJ
Department of Chemistry, University of Illinois, 600 South Matthews Avenue, Urbana, Illinois 61801, USA.
Marković
Dean
D
Ueda
Mitsuhiro
M
Hartwig
John F
JF
D000498:Allyl Compounds / Q000737:chemistry*; D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D002219:Carbamates / Q000737:chemistry*; D002254:Carbonates / Q000737:chemistry; D002384:Catalysis; D020650:Combinatorial Chemistry Techniques; D007202:Indicators and Reagents; D007495:Iridium / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry; D013237:Stereoisomerism
D000498:Allyl Compounds; D000588:Amines; D002219:Carbamates; D002254:Carbonates; D007202:Indicators and Reagents; D009942:Organometallic Compounds; D007495:Iridium; D010165:Palladium