Chiral phosphinooxazolidine ligands for palladium- and platinum-catalyzed asymmetric Diels-Alder reactions.
Cationic palladium (Pd)- and platinum (Pt)-phosphinooxazolidine catalysts 13a-c, 15a-d, 17a-c, and 19a-c were prepared from phosphinooxazolidine ligands 1-3, MCl(2) (M = Pd and Pt), and counterions, and the activities of the catalysts in the asymmetric Diels-Alder (DA) reactions of cyclic or acyclic dienes with imide dienophiles were investigated. These catalysts demonstrated high levels of catalytic activity. The cationic Pd-POZ complex 13c provided particularly excellent enantioselectivity (98% ee) in the DA reactions of cyclopentadiene with acryloyl-, crotonyl-, and fumaroyl-1,3-oxazolidin-2-ones (20a-c).
Nakano
Hiroto
H
Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan. hnakano@tohoku-pharm.ac.jp
Takahashi
Kouichi
K
Okuyama
Yuko
Y
Senoo
Chieko
C
Tsugawa
Natsumi
N
Suzuki
Yuichiro
Y
Fujita
Reiko
R
Sasaki
Kazuo
K
Kabuto
Chizuko
C