Knopf Ioana, Tofan Daniel, Beetstra Dirk, Al-Nezari Abdulaziz, Al-Bahily Khalid, Cummins Christopher C
Department of Chemistry , Massachusetts Institute of Technology , 77 Massachusetts Avenue , Cambridge , MA 02139-4307 , USA . Email:
SABIC CRD , Fundamental Catalysis , Thuwal 23955-6900 , Saudi Arabia.
Chem Sci. 2017 Feb 1;8(2):1463-1468. doi: 10.1039/c6sc03614g. Epub 2016 Oct 11.
A family of -macrocyclic diphosphines was prepared in just three steps from white phosphorus and commercial materials using a modular synthetic approach. Alkylation of bicyclic diphosphane 3,4,8,9-tetramethyl-1,6-diphosphabicyclo(4.4.0)deca-3,8-diene, or P(dmb), produced phosphino-phosphonium salts [R-P(dmb)]X, where R is methyl, benzyl and isobutyl, in yields of 90-96%. Treatment of these salts with organolithium or Grignard reagents yielded symmetric and unsymmetric macrocyclic diphosphines of the form -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 Cy-DPC was synthesized in 74% yield from the dichlorodiphosphine ClP(dmb). As a first application, these -macrocyclic diphosphines were used as ligands in the nickel-catalyzed synthesis of acrylate from CO and ethylene, for which they showed promising catalytic activity.
通过模块化合成方法，仅用三步就从白磷和市售原料制备了一族 - 大环二膦。双环二膦烷3,4,8,9 - 四甲基 - 1,6 - 二磷杂双环(4.4.0)癸 - 3,8 - 二烯（即P(dmb)）的烷基化反应生成了膦基 - 鏻盐[R - P(dmb)]X，其中R为甲基、苄基和异丁基，产率为90 - 96%。用有机锂试剂或格氏试剂处理这些盐，得到了对称和不对称的大环二膦，其形式为 - 1 - R - 6 - R'- 3,4,8,9 - 四甲基 - 2,5,7,10 - 四氢 - 1,6 - 二磷杂环辛四烯（即R,R'- DPC），其中R'为甲基、环己基、苯基或均三甲苯基，产率为46 - 94%。另外，对称二膦Cy - DPC由二氯二膦ClP(dmb)合成，产率为74%。作为首次应用，这些 - 大环二膦被用作镍催化由CO和乙烯合成丙烯酸酯的配体，它们在该反应中表现出了有前景的催化活性。
