Chiral phosphinooxazolidine ligands for palladium- and platinum-catalyzed asymmetric Diels-Alder reactions

Hiroto Nakano; Kouichi Takahashi; Yuko Okuyama; Chieko Senoo; Natsumi Tsugawa; Yuichiro Suzuki; Reiko Fujita; Kazuo Sasaki; Chizuko Kabuto

doi:10.1021/jo049375j

Chiral phosphinooxazolidine ligands for palladium- and platinum-catalyzed asymmetric Diels-Alder reactions

J Org Chem. 2004 Oct 15;69(21):7092-100. doi: 10.1021/jo049375j.

Authors

Hiroto Nakano¹, Kouichi Takahashi, Yuko Okuyama, Chieko Senoo, Natsumi Tsugawa, Yuichiro Suzuki, Reiko Fujita, Kazuo Sasaki, Chizuko Kabuto

Affiliation

¹ Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan. hnakano@tohoku-pharm.ac.jp

PMID: 15471457
DOI: 10.1021/jo049375j

Abstract

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).