Pd(II)-catalyzed asymmetric addition of malonates to dihydroisoquinolines.
We have developed a highly efficient reaction for catalytic asymmetric addition of malonates to dihydroisoquinolines using chiral Pd(II) complexes. In the reactions, substrates with various substitution patterns were available, and the reactions were complete within several hours (<3 h in most cases) under mild reaction conditions, affording various optically active C1-substituted tetrahydroisoquinoline derivatives (up to 98% yield, up to 97% ee). Furthermore, slow addition of DDQ allowed the in situ generation of the reactive intermediate from the corresponding N-Boc-protected amine, and dehydrogenative addition reaction was successfully demonstrated.
Sasamoto
Naoki
N
IMRAM, Tohoku University, Miyagi 980-8577, Japan.
Dubs
Christian
C
Hamashima
Yoshitaka
Y
Sodeoka
Mikiko
M
D002384:Catalysis; D007546:Isoquinolines / Q000737:chemistry*; D008314:Malonates / Q000737:chemistry*; D008958:Models, Molecular; D010165:Palladium / Q000737:chemistry*
C109853:G 1617; D007546:Isoquinolines; D008314:Malonates; D010165:Palladium; C030290:malonic acid