新的手性配体促进的二芳基二酸和联萘酚的不对称合成

New Asymmetric Synthesis of Several Biaryl Diacids and Dinaphthol via Biaryl Coupling Reaction Induced by Chiral Auxiliaries

由手性配体α D 葡萄糖衍生物 5 ,6 ,7以及薄荷醇 (8)和葑醇 (9) ,经Ullmann偶联反应得到光学活性的 (R) 和 (S) 6 ,6′ 二硝基联苯 2 ,2′ 二甲酸 (4a) ,(R) 6 ,6′ 二甲基联苯 2 ,2′ 二甲酸 (4b) ,(R) 1,1′ 联萘 2 ,2′ 二甲酸(13) .以三个手性膦酰胺 16 ,17,18和CuCl组成的手性络合物为催化剂 ,通过 2 萘酚直接氧化偶联得到 (S) 2 ,2′ 联萘酚 (15 ) .产物 4,13,15具有中等ee值的光学活性 .

Optically active (R)- and (S)-6,6'-dinitrobiphenyl-2,2'-dicarboxylic acid (4a), (R)-6,6'-dimethylbiphenyl 2,2-dicarboxylic acid (4b), (R)-1,1'-binaphthyl-2,2'-dicarboxyhe acid (13) were synthesized by the asymmetric Ullmann coupling reaction induced by derivatives of alpha-D-glucose 5, 6, 7, menthol (8), fenchol (9). (S)-2,2'-Binapthol (15) was prepared from 2-napthol via an oxidative coupling reaction catalyzed by three chiral complexes prepared in situ from CuCl (10 mol%) and chiral phosphoramides 16, 17, 18. The products 4, 13 and 15 have moderate ee values.