A family of cis-macrocyclic diphosphines: modular, stereoselective synthesis and application in catalytic CO<sub>2</sub>/ethylene coupling
作者:Ioana Knopf、Daniel Tofan、Dirk Beetstra、Abdulaziz Al-Nezari、Khalid Al-Bahily、Christopher C. Cummins
DOI:10.1039/c6sc03614g
日期:——
unsymmetric macrocyclic diphosphines of the form cis-1-R-6-R′-3,4,8,9-tetramethyl-2,5,7,10-tetrahydro-1,6-DiPhospheCine, or R,R′-DPC, in which R′ is methyl, cyclohexyl, phenyl or mesityl, in yields of 46–94%. Alternatively, symmetric diphosphine Cy2-DPC was synthesized in 74% yield from the dichlorodiphosphine Cl2P2(dmb)2. As a first application, these cis-macrocyclic diphosphines were used as ligands
使用模块化合成方法,仅需三步即可从白磷和商业原料制得一个顺式-大环二膦家族。双环二膦3,4,8,9-四甲基-1,6-二磷双环(4.4.0)癸3,8-二烯或P 2(dmb)2的烷基化反应,生成膦膦盐[RP 2(dmb )2 ] X,其中R为甲基,苄基和异丁基,产率90-96%。用有机锂或格氏试剂处理这些盐可得到顺式对称和不对称的大环二膦-1-R-6-R'-3,4,8,9-四甲基-2,5,7,10-四氢-1,6-二苯基膦或R,R'-DPC,其中R'为甲基,环己基,苯基或三甲苯基,收率46-94%。或者,由二氯二膦Cl 2 P 2(dmb)2以74%的收率合成对称的二膦Cy 2 -DPC 。作为第一个应用,这些顺式-大环二膦用作配体在镍催化的由CO 2和乙烯合成丙烯酸酯的过程中显示出了令人鼓舞的催化活性。