Development of Asymmetric Reactions Catalyzed by Chiral Bronsted Acid

我们已经开发合成了以(R)-BINOL为起始原料的手性磷酸双酯，并展示了其作为手性Bronsted酸的催化活性。为了扩展手性Bronsted酸催化，我们研究了亚胺的不对称亲核加成和环加成反应。亚磷酸二异丙酯与乙二胺的亲核加成反应在3，3‘-位含3，5-(CF_3)C_6H_2基团的磷酸双酯催化下进行，得到了具有高对映选择性的α-氨基磷酸酯。高电子含量的二烯如丹尼舍夫斯基的二烯与乙二胺的氮杂Diels-Alder反应顺利地进行，得到了具有较高对映异电子活性的含氮六元环。富电子的烯烃与氮杂二烯的反向需要电子的aza-Diels-Alder反应也顺利地进行，得到了具有良好的对映选择性的四氢喹啉衍生物在3，3‘-位上含有9-苯基的磷酸双酯。由(R)-BINOL衍生而来，作为手性Bransted酸，在亲核反应和环加成反应中表现出优异的催化活性，从而得到具有良好到优异光学纯度的含氮化合物。

We already developed and synthesized a chiral phosphoric acid diester starting from (R)-BINOL and demonstrated its catalytic activity as a chiral Bronsted acid. In order to extend the chiral Bronsted acid catalysis, we have studied the enantioselective nucleophilic addition and cycloaddition reaction toward imines.Nucleophilic addition of diisopropyl phosphite with aldimine was catalyzed by a phosphoric acid diester bearing 3,5-(CF_3)C_6H_2 groups on 3,3'-position to give a-aminophosphonate with high enantioselectivity.Aza Diels-Alder reaction of electron-rich dienes such as Danishefsky's diene with aldimine proceeded smoothly to give nitrogen-containing 6-membered rings with high to excellent enantioselectivity.The reverse electron-demand aza Diels-Alder reaction of electron-rich alkene with aza Diene also proceeded smoothly to give tetrahydroquinoline derivatives with excellent enantioselectivity by means of a phosphoric acid diester bearing 9-anthryl group on the 3,3'-positions.We have found that the phosphoric acid diesters, derived from (R)-BINOL, exhibit excellent catalytic activity as chiral Bransted acid for the nucleophilic reactions and cycloaddition reactions to give nitrogen-containing compounds with good to excellent optical purity.