Design of Novel Amphoteric Chiral Ligands and their Use for Catalytic Asymmetric Synthesis

设计并合成了一类新的含羧基、羟基等功能基团的光学活性膦和恶唑啉化合物。在配体中，双恶唑啉-联萘衍生物作为手性配体用于钯（II）催化的邻烯丙基苯酚的不对称Wacker型环化反应。因此，催化不对称Wacker型环化2-（2，3-二甲基-2-丁烯基）苯酚在10摩尔%的手性钯（II）催化剂存在下进行反应，所述手性钯（II）催化剂由Pd（OCOCF_3）_2和（S，S）-2，2 ′-双[4-（烷基）恶唑基]-1，1 ′-联萘（S，（S）-boxax）与对苯醌在甲醇中于60 ℃反应24 h，得到（S）-（-）-2-甲基-2-异丙烯基-2，3-二氢苯并呋喃，产率为75%，ee值为96%。

New class of optically active phosphines and oxazolines having fuctional groups (e.g.carboxyl, hydroxy) were designed and prepared. Of the ligands, the bisoxazoline-binaphthyl derivatives found utility as chiral ligands for palladium (II)-catalyzed asymmetric Wacker-type Cyclization of o-allylphenols. Thus, catalytic asymmetric Wacker-type cyclization of 2-(2,3-dimethyl-2-butenyl) phenol in the presence of 10 mol % of a chiral palladium (II) catalyst prepared from Pd (OCOCF_3)_2 and (S,S)-2,2'-bis[4-(alkyl)oxazolyl]-1,1'-binaphthyl (S,S)-boxax) and rho-benzoquinone in methanol at 60ﾟC for 24h gave 75% yield of (S)-(-)-2-methyl-2-isopropenyl-2,3-dihydrobenzofuran of 96% ee.