Page 132 - 《精细化工》2020年第9期
P. 132

·1846·                            精细化工   FINE CHEMICALS                                 第 37 卷

            性,利于实现对 CO 2 、Togni′s ReagentⅡ的固定和活                    under ambient conditions[J]. ACS Catalysis, 2018, 8(1): 419-450.
                                                               [4]   SZE N D, KO M K W. Carbon disulfide and carbonyl sulfide in the
            化作用。在 DBU 的脱质子作用下,烯丙基胺底物与                              stratospheric sulfur budget[J]. Nature, 1979, 280(5720): 308-310.
            孔道内 CO 2 加成得到氨基甲酸酯中间体 B。如中间                        [5]   SMITH  G  V,  BARTÓK  M,  NOTHEISZ  F,  et al.  Determination  of
                                                                   active sites on palladium by carbon disulfide titration[J]. Journal of
            态物质 C 所示,Togni′s Reagent  Ⅱ被铜节点吸附、                     Catalysis, 1988, 110(1): 203-205.
                                                               [6]   FURUYA  T,  KAMLET  A  S,  RITTER  T.  Catalysis  for  fluorination
            活化,使碘中心带有部分正电荷;铜节点可能将一                                 and trifluoromethylation[J]. Nature, 2011, 473(7348): 470-477.
            个电子转移给锚定的 Togni′s Reagent  Ⅱ,使其发生                  [7]   YE J H,  SONG  L, ZHOU W J,  et al.  Selective
                                                                   oxytrifluoromethylation  of  allylamines  with  CO 2[J].  Angewandte
            I—CF 3 键均裂,并将三氟甲基自由基加成到邻近底                             Chemie International Edition, 2016, 55(34): 10022-10026.
            物 1a 的烯烃片段,生成碳中心自由基中间态 D;接                         [8]   DRAKE T, JI P, LIN W. Site isolation in metal-organic frameworks
                                                                   enables  novel  transition  metal  catalysis[J].  Accounts  of  Chemical
            下来,自由基中间态 D 经过与铜节点的氧化还原过                               Research, 2018, 51(9): 2129-2138.
            程使铜中心恢复初始价态,同时如中间态 E 所示,                           [9]   LIAN X, FANG Y, JOSEPH E, et al. Enzyme-MOF (metal-organic
                                                                   framework) composites[J]. Chemical Society Reviews, 2017, 46(11):
            发生环合得到吸附于孔道内的最终产物。随后,通                                 3386-3401.
                                                               [10]  CUI Y J, LI B, HE H J, et al. Metal-organic frameworks as platforms
            过外来底物、CO 2 、Togni′s ReagentⅡ的竞争性配位                     for  functional  materials[J].  Accounts  of  Chemical  Research,  2016,
            作用,产物 2a 发生脱附,游离出孔道,反应进入下                              49(3): 483-493.
                                                               [11]  WANG  C,  LIU  D  M,  LIN  W  B.  Metal-organic  frameworks  as  a
            一个催化循环。                                                tunable  platform  for  designing  functional  molecular  materials[J].
                                                                   Journal  of  the  American  Chemical  Society,  2013,  135(36):  13222-
                                                                   13234.
            3    结论                                            [12]  LIU J W,  CHEN  L F,  CUI  H,  et al.  Applications of  metal-organic
                                                                   frameworks in heterogeneous supramolecular catalysis[J]. Chemical
                (1)实现了利用晶态铜基 MOF 材料 HKUST-1                        Society Reviews, 2014, 43(16): 6011-6061.
                                                               [13]  CHUI S, LO S, CHARMANT J, et al. A chemically functionalizable
            作为非均相催化剂,催化烯丙基胺类底物与三氟甲                                 nanoporous  material  [Cu 3(TMA) 2(H 2O) 3] n[J].  Science,  1999,
            基前体 Togni′s Reagent  Ⅱ常压下的 CO 2 反应,制得                  283(5405): 1148-1150.
                                                               [14]  FURUKAWA  H,  CORDOVA  K  E,  O’KEEFFE  M,  et al.  The
            药物功能性杂环分子 2-三氟甲基-唑烷酮衍生物。                              chemistry and applications of metal-organic frameworks[J]. Science,
                (2)条件优化及控制实验确定了适用于烯丙基                              2013, 341(6149): 1230444.
                                                               [15]  QI B, ZHANG T X, LI M C, et al. Highly shape- and regio-selective
            胺类底物的最优反应条件;探索了具有不同取代基                                 peroxy-trifluoromethylation  of  styrene  by  metal-organic  framework
                                                                   Cu 3(BTC) 2[J]. Catalysis Science & Technology, 2017, 7(24): 5872-5881.
            团底物的适用范围,底物中与烯烃相连的苯基上的                             [16]  KAWAMURA S, EGAMI H, SODEOKA M. Aminotrifluoromethylation
            吸电子基团能够提高反应转化率,而给电子效应则                                 of  olefins via  cyclic  amine  formation:  Mechanistic  study  and
                                                                   application  to  synthesis  of  trifluoromethylated  pyrrolidines[J].
            会降低反应活性,即使底物烯烃附近具有较大的空                                 Journal of the American Chemical Society, 2015, 137(14): 4865-4873.
            间位阻基团,反应仍具有良好的效果。相较于传统                             [17]  KENDA B,  TURET  L, QUESNEL L,  et al.  New  heterocyclic
                                                                   derivatives  useful  for  the  treatment  of  CNS  disorders:
            的催化合成路径,该反应使用更低的催化剂负载量,                                WO2008132139 [P]. 2008-11-06.
                                                               [18]  TOVAR  T  M,  ZHAO  J  J,  NUNN  W  T,  et al.  Diffusion  of  CO 2 in
            且非均相催化剂 HKUST-1 使用后可回收,经 4 次循
                                                                   large crystals of Cu-BTC MOF[J]. Journal of the American Chemical
            环使用依然具有良好的催化效果、并保持晶态结构,                                Society, 2016, 138: 11449-11452.
                                                               [19]  MENG  Q  Y,  SCHIRMER  T  E,  KATOU  K,  et al.  Controllable
            证实了晶态 HKUST-1 材料良好的结构稳定性。                              isomerization  of  alkenes  by  dual  visible-light-cobalt  catalysis[J].
                (3)HKUST-1 良好的孔隙率有利于反应的传质                          Angewandte Chemie International Edition, 2019, 58(17): 5723-5728.
                                                               [20]  DONG  X,  HAN  Y,  YAN  F  C,  et al.  Palladium-catalyzed  6-endo
            过程,具有路易斯酸性空配位的铜节点作为 MOF                                selective  alkyl-heck  reactions:  Access  to  5-phenyl-1,2,3,6-
            材料的催化活性中心,利于 CO 2 、Togni′s Reagent  Ⅱ                  tetrahydropyridine  derivatives[J].  Organic  Letters,  2016,  18(15):
                                                                   3774-3777.
            等的锚定、活化,反应物之间的空间隔离也有助于                             [21]  BARLUENGA J, FAÑANAS F J, SANZ R,  et al. 2-Arylallyl as a
            实现不同反应步骤的区位化,避免无效碰撞、减少                                 new protecting group for amines, amides and alcohols[J]. Chemical
                                                                   Communications, 2005, 7: 933-935.
            副反应,体现了非均相催化体系的优势。                                 [22]  YAMANAKA H, MATSUO J-I, KAWANA A, et al. New methods
                                                                   for  the  preparations  of  2-arylaziridines,  α-imidostyrenes,  and
                (4)当采用 CS 2 作为碳源时,用一步法合成出                          allylamines  from  olefins  via  diphenylvinylsulfonium  triflates[J].
            具有调节中枢神经系统功能的药物分子衍生物,显                                 Arkivoc, 2003, (Ⅲ): 42-65.
                                                               [23]  VEERANNA K D, DAS K K, BASKARAN S. One-pot synthesis of
            示出 HKUST-1 对硫毒化作用的耐受性,克服了传统                            cyclopropane-fused  cyclic  amidines:  An  oxidative  carbanion
            金属盐均相催化体系的不足,进一步揭示了该非均                                 cyclization[J].  Angewandte  Chemie  International  Edition,  2017,
                                                                   56(51): 16197-16201.
            相催化体系的工业应用潜力。                                      [24]  YU  D  G  (余达刚),  YE  J  H  (叶剑衡),  YAN  S  S  (颜思顺),  et al.
                                                                   Fluorine-containing heterocyclic compound and preparation method:
            参考文献:                                                  CN106220581[P]. 2016-12-14.
                                                               [25]  SCHAFER L,  ROSCA  S-C, DIPUCCHIO R,  et al.  Group  5  metal
            [1]   MÜLLER K, FAEH C, DIEDERICH F. Fluorine in pharmaceuticals:   complexes  for  catalytic  amine  functionalization:  WO2018213938
                 Looking beyond intuition[J]. Science, 2007, 317(5846): 1881-1886.     [P]. 2018-11-29.
            [2]   SAKAKURA T, CHOI J C, YASUDA H. Transformation of carbon   [26]  WANG  F,  WANG  D  H,  MU  X,  et al.  Copper-catalyzed
                 dioxide[J]. Chemical Reviews, 2007, 107(6): 2365-2387.     intermolecular trifluoromethylarylation of alkenes: Mutual activation
                                                                                     +
            [3]   SHAIKH R R, PORNPRAPROM S, D′ELIA V. Catalytic strategies   of  arylboronic  acid  and  CF 3  reagent[J].  Journal  of  the  American
                 for  the  cycloaddition  of  pure,  diluted,  and  waste  CO 2  to  epoxides   Chemical Society, 2014, 136(29): 10202-10205.
   127   128   129   130   131   132   133   134   135   136   137