Asymmetric Synthesis of Tetrahydroquinolines with Quaternary Stereocenters through the Povarov Reaction

作者：Xie Mingsheng; Liu Xiaohua; Zhu Yin; Zhao Xiaohu; Xia Yong; Lin Lili; Feng Xiaoming^*

来源：Chemistry - A European Journal, 2011, 17(49): 13800-13805.

DOI：10.1002/chem.201102333

• asymmetric catalysis
• dioxides
• Povarov reaction
• scandium
• tetrahydroquinolines

The asymmetric Povarov reaction with a-alkyl styrenes as dienophiles was catalyzed by an N,N'-dioxide L4Sc(OTf)3 complex. Enantiopure tetrahydroquinoline derivatives with a quaternary stereocenter at the C4 position were synthesized for the first time. A wide variety of a-alkyl styrenes and N-aryl aldimines were tolerated in the reaction, to give excellent diastereo- (up to 99:1 d.r.) and enantioselectivities (92 to >99?% ee). In addition, the reaction could be performed on the gram scale without any loss of yield, diastereoselectivity, or enantioselectivity. An intermolecular hydrogen-shift reaction was found to be a side reaction, which offered a method to synthesize the corresponding quinoline derivatives with chiral quaternary sterocenters.

• 出版日期2011-12
• 单位四川大学