Page 252 - 201905
P. 252

·1020·                            精细化工   FINE CHEMICALS                                  第 36 卷

            与 DPBA 反应 30 min,产率为 99%(序号 7)。DPBA                    coupling reactions in total synthesis[J]. Angew Chem Int Ed, 2005,
            与 3-溴喹啉反应 120 min 产率也可得到 77%(序号 8)。                    44(29): 4442-4489.
                                                               [5]   Miyaura N, Yamada K, Suzuki A. A new stereospecific cross-
                 其他溴代氮杂芳烃底物,如 5-溴嘧啶与 DPBA                          coupling by the palladium-catalyzed reaction of 1-alkenylboranes with
            反应 10 h,产率为 89%(序号 10)。值得注意的是,                         1-alkenyl  or  1-alkynyl  halides[J].  Tetrahedron  Lett,  1979,  20(36):
                                                                   3437-3440.
            该催化反应体系也可用于溴代硫杂芳烃与 DPBA 的                          [6]   Wu X, Anbarasan P, Neumann H, et al. From noble metal to nobel
            SM 反应,2-溴噻吩在 30 min 内反应完全,产率为                          prize:  palladium-catalyzed  coupling  reactions  as  key  methods  in
                                                                   organic synthesis[J]. Angew Chem Int Ed, 2010, 49(48): 9047-9050.
            92%(序号 11)。3-溴噻吩与 DPBA 的 SM 反应,虽
                                                               [7]   Johansson  Seechurn  C  C,  Kitching  M  O,  Colacot  T  J,  et al.
            然其反应活性较 2-溴噻吩低,但也能得到中等以上                               Palladium-catalyzed cross-coupling: A historical contextual perspective
            的产率(序号 12)。此外,2-氯吡嗪与 DPBA 反应                           to  the  2010  nobel  prize[J].  Angew  Chem  Int  Ed,  2012,  51(21):
                                                                   5062-5085.
            120 min 亦可得到 89%的产率(序号 9)。从上述结                     [8]   Han W, Liu C, Jin Z. In situ generation of palladium nanoparticles: a
            果可以看出,2-溴吡啶、2-溴喹啉以及 2-溴噻吩的                             simple  and  highly  active  protocol  for  oxygen-promoted  ligand-free
                                                                   Suzuki coupling reaction of aryl chlorides[J]. Org Lett, 2007, 9(20):
            反应活性均分别高于 3-溴吡啶、3-溴喹啉和 3-溴噻                            4005-4007.
            吩,其原因可能是邻位效应促进了反应的进行。                              [9]   Liu  C,  Yang  W.  A  fast  and  oxygen-promoted  protocol  for  the
                                                                   ligand-free  Suzuki  reaction  of  2-halogenated  pyridines  in  aqueous
                 以上结果表明,该催化反应体系对芳杂环卤代
                                                                   media[J]. Chem Commun, 2009, (41): 6267-6269.
            物与 DPBA 的 Suzuki-Miyaura 交叉偶联反应具有较                 [10]  Yang W, Liu C, Qiu J. In situ formation of N, O-bidentate ligand via
            高的活性,是合成芳杂环取代三苯胺衍生物的有效                                 the  hydrogen  bond  for  highly  efficient  Suzuki  reaction  of  aryl
                                                                   chlorides[J]. Chem Commun, 2010, 46(15): 2659-2661.
            方法。                                                [11]  Liu C, Han N, Song X, et al. A general and highly efficient method
                                                                   for the construction of aryl-substituted N-heteroarenes[J]. Eur J Org
            3    结论                                                chem, 2010, (29): 5548-5551.
                                                               [12]  Liu C, Zhang Y, Liu N, et al. A simple and efficient approach for the
                                                                   palladium-catalyzed  ligand-free  Suzuki  reaction  in  water[J].  Green
                 (1)以 2-溴吡啶和 4-硼酸三苯胺的 Suzuki-
                                                                   Chem, 2012, 14(11): 2999-3003.
            Miyaura 反应作为模板反应,获得了最优反应条件:                        [13]  Shirota  Y,  Kageyama  H.  Charge  carrier  transporting  molecular
            空 气中, 80  ℃, 2- 溴吡 啶 0.25  mmol , DPBA                 materials  and  their  applications  in  devices[J].  Chem  Rev,  2007,
                                                                   107(4): 953-1010.
            0.375 mmol,Pd/C 占 2-溴吡啶物质的量的 1.5%,K 2 CO 3         [14]  Fang  Z,  Teo  T  L,  Cai  L,  et al.  Bridged  triphenylamine-based
            0.5 mmol,乙醇水溶液 4 mL〔V(乙醇)∶V(水)                         dendrimers:  tuning  enhanced  two-photon  absorption  performance
                                                                   with locked molecular planarity[J]. Org Lett, 2009, 11(1): 1-4.
            =  3∶1〕。在最优反应条件下,合成了 12 个芳杂环                       [15]  Walzer  K,  Maennig  B,  Pfeiffer  M,  et al.  Highly  efficient  organic
            取代的三苯胺衍生物,最高收率达 99%。                                   devices  based  on  electrically  doped  transport  layers[J].  Chem  Rev,
                 (2)本文发展的合成三苯胺衍生物的方法不需                             2007, 107(4): 1233-1271.
                                                               [16]  Hagfeldt A, Boschloo G, Sun L, et al. Dye-sensitized solar cells[J].
            要惰性气体保护、无需外加配体或促进剂、反应介                                 Chem Rev, 2010, 110(11): 6595-6663.
            质环境友好、反应条件温和且底物适用广泛,为具                             [17]  Ono K, Joho M, Saito K, et al. Synthesis and electroluminescence
                                                                   properties offac-tris(2-phenylpyridine)iridium derivatives containing
            有重要应用价值的芳杂环取代三苯胺衍生物提供了                                 hole-trapping moieties[J]. Eur J Inorg Chem, 2006, (18): 3676-3683.
            简便、环境友好的合成方法,具有潜在的应用前景。                            [18]  Lu J, Liu Q, Ding J, et al. New triscyclometalated iridium complexes
                                                                   for  applications  in  phosphorescent  light-emitting  diodes[J].  Synth
            参考文献:                                                  Met, 2008, 158(3): 95-103.
                                                               [19]  Mak C S, Pentlehner D, Stich M, et al. Exceptional oxygen sensing
            [1]   Nicolaou  K  C,  Bulger  P  G,  Sarlah  D.  Metathesis  reactions  in total   capabilities  and  triplet  state  properties  of  Ir(ppy-NPh 2) 3[J].  Chem
                 synthesis[J]. Angew Chem Int Ed, 2005, 44(29): 4490-4527.     Mater, 2009, 21(11): 2173-2175.
            [2]   Miyaura N, Suzuki A. Palladium-catalyzed cross-coupling reactions   [20]  Marck G, Villiger A, Buchecker R. Aryl couplings with heterogeneous
                 of organoboron compounds[J]. Chem Rev, 1995, 95(7): 2457-2483.     palladium catalysts[J]. Tetrahedron Lett, 1994, 35(20): 3277-3280.
            [3]   Sonogashira  K,  Tohda  Y,  Hagihara  N.  A  convenient  synthesis  of   [21]  Felpin  F  X,  Ayad  T,  Mitra  S.  Pd/C: An  old  catalyst  for  new
                 acetylenes: Catalytic  substitutions  of  acetylenic  hydrogen  with   applications:  Its  use  for  the  Suzuki-Miyaura  reaction[J].  Eur  J Org
                 bromoalkenes, iodoarenes and bromopyridines[J]. Tetrahedron Lett,   Chem, 2006, (12): 2679-2690.
                 1975, 16(50): 4467-4470.                      [22]  Seki  M.  Recent  advances  in  Pd/C-catalyzed  coupling  reactions[J].
            [4]   Nicolaou  K  C,  Bulger  P  G,  Sarlah  D.  Palladium-catalyzed  cross-   Synthesis, 2006, 18: 2975-2992.
   247   248   249   250   251   252   253   254   255   256   257