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·986·                             精细化工   FINE CHEMICALS                                 第 40 卷

            Ru、Pd、Rh、Ir 等贵金属在该领域表现出优异的催                            Regional Meeting, 2013: 209-225.
                                                               [4]   GHAFFAR T,  CHARMANT J P, SUNLEY G J,  et al. Methane
            化效果,但随着环境问题的加重,贵金属毒性大的
                                                                   formation  during  the iridium/iodide catalysed carbonylation of
            问题日益凸显,环境友好、自然储量丰富的碱土金                                 methanol[J]. Inorganic Chemistry Communications, 2000, 3(1): 11-12.
            属以及廉价过渡金属开始尝试应用于催化不饱和烃                             [5]   NEEVE E  C, GEIER S J, MKHALIDK I A,  et al. Diboron  (4)
                                                                   compounds: Fom  structural curiosity to synthetic workhorse[J].
            的硼氢化反应。很多含有这类金属的催化剂在活性                                 Chemical Reviews, 2016, 116(16): 9091-9161.
            和选择性方面与贵金属催化剂相当。更重要的是,                             [6]   BAGUTSKI  V, FRENCH R M,  AGGARWAL V K.  Full  chirality
                                                                   transfer in the conversion of secondary alcohols into tertiary boronic
            它们高丰度、低价格、环境友好的特点更符合绿色
                                                                   esters  and  alcohols using lithiation-orylation reactions[J]. Angewandte
            化学以及工业化发展的要求。然而,此类金属基催                                 Chemie Iernational Edition, 2010, 122(30): 5268-5271.
            化剂仍有许多问题需解决,距取代贵金属基催化剂                             [7]   MLYNARSKI S N, KARNS A S, MORKEN J P. Direct stereospecific
                                                                   amination of alkyl and aryl pinacol  boronates[J]. Journal of the
            在该领域的地位还有很长距离:(1)底物普适性较                                American Chemical Society, 2013, 134(12): 16449-16451.
            差,已发表的报道显示,当底物含有羟基、羧基和                             [8]   RAO  Y L, WANG S N. Four-coordinate organoboron compounds
                                                                   with a π-conjugated chelate ligand for optoelectronic applications[J].
            硝基时,催化剂催化活性不佳;(2)反应的区域选                                Inorganic Chemistry, 2011, 50(24): 12263-12274.
            择性大多为 末端烯烃或末端炔烃,其产物也以                              [9]   MIAO J H, WANG Y H, LIU J, et al. Organoboron molecules and
            Anti-Markovnikov 型为主,对内部不饱和烃以及生成                       polymers for  organic solar cell applications[J]. Chemical Society
                                                                   Reviews, 2021, 51(1): 153-187.
            Markovnikov 型产物的硼氢化反应仍是难点之一;                       [10]  BROWN H C, RAO B. A new powerful reducing agent—Sdium
            (3)对廉价金属基催化剂的机理研究不足,许多机                                borohydride in the presence of aluminum chloride and other polyvalent
                                                                   metal halides1,2[J]. Macmillan, 1956, 78(11): 2582-2588.
            理是在贵金属基催化剂催化知识的基础上提出的,
                                                               [11]  DHILLON R S. Hydroboration and organic synthesis: 9-Borabicyclo
            并且大多还停留在推测阶段。                                          [3.3.1]nonane (9-BBN)[M]. Springer  Science & Business Media,
                 针对这些问题,可以采用以下措施:首先,需                              2007.
                                                               [12]  CARROLL A M, O'SULLIVAN T P, GUIRY P J. The development
            要开发更多的有机配体,利用其与金属的协同作用                                 of enantioselective rhodium-catalysed hydroboration  of  olefins[J].
            来提高底物的适用范围以及反应的选择性;而对于                                 Advanced Synthesis & Catalysis, 2005, 347(5): 609-631.
                                                               [13]  BELETSKAYA I, PELTER A. Hydroborations catalysed by transition
            无配体催化体系,可通过改变加入溶剂和碱的种类,                                metal complexes[J]. Tetrahedron, 1997, 53(14): 4957-5026.
            达到区域选择性控制的目的,因此这也需要建立起                             [14]  MÄNNIG D, NÖTH H. Catalytic  hydroboration with rhodium
                                                                   complexes[J]. Angewandte Chemie  International Edition, 1985,
            一个金属中心、溶剂、硼化试剂和碱的数据库,方
                                                                   24(10): 878-879.
            便找到最优的搭配组合;可以利用 DFT 计算探讨机                          [15]  SHEGAVI M L,  BOSE S K. Recent advances in the catalytic
            理,如 GUO 等    [84] 和 FU 等 [85] 就通过理论计算研究了               hydroboration of carbonyl compounds[J]. Catalysis Science &
                                                                   Technology, 2019, 9(13): 3307-3336.
            Cu、Fe 等金属基催化剂催化 1,3-丁二烯硼氢化以及                       [16]  WEETMAN C, HILL M S, MAHON M F. Magnesium-catalysed
            硼氰化反应的催化机理。因此,相比于传统的贵金                                 hydroboration of isonitriles[J]. Chemical Communications, 2015,
                                                                   51(77): 14477-14480.
            属基催化剂,碱土金属以及廉价过渡金属基催化剂
                                                               [17]  CAO X, WANG W F, LU K, et al. Magnesium-catalyzed hydroboration
            在催化不饱和烃的硼氢化反应领域具有更大的发展                                 of organic carbonates, carbon dioxide and esters[J]. Dalton Transactions,
            空间,有望取代贵金属应用于实验室及工业生产中。                                2020, 49(9): 2776-2780.
                                                               [18]  FALCONNET A, MAGRE M, MAITY B,  et al. Asymmetric
                 此外,同样含金属中心的金属有机框架材料也                              magnesium-catalyzed hydroboration  by metal-ligand cooperative
            广泛地应用于有机催化反应中,但在硼氢化反应领                                 catalysis[J]. Angewandte Chemie Iernational Edition, 2019, 131(49):
                                                                   17731-17735.
            域却鲜有报道,其独特结构决定其既可以直接进行
                                                               [19]  YADAV S, PAHAR S, SEN S S.  Benz-amidinato calcium iodide
            催化,也可以作为均相催化剂的载体,还能通过配                                 catalyzed  aldehyde and ketone hydroboration with unprecedented
            位有机配体或金属增强自身催化性能,此材料为硼                                 functional  group tolerance[J]. Chemical Communications, 2017,
                                                                   53(33): 4562-4564.
            氢化反应提供了新思路,有着极大的发展潜力。                              [20]  BURGESS K, OHLMEYER M J. Transition-metal promoted
                                                                   hydroborations of alkenes, emerging methodology for organic
            参考文献:                                                  transformations[J]. Chemical Reviews, 1991, 91(6): 1179-1191.
            [1]   YANG C T, ZHANG Z Q, TAJUDDIN H, et al. Alkylboronic esters   [21]  VOGELS C M,  WESTCOTT S A. Recent advances in organic
                 from copper-catalyzed borylation of primary  and secondary alkyl   synthesis using transition metal-catalyzed hydroborations[J]. Current
                 halides and  pseudohalides[J]. Angewandte Chemie Iernational Edition,   Organic Chemistry, 2005, 9(7): 687-699.
                 2012, 51(2): 528-532.                         [22]  CHONG  C C, KINJO R. Catalytic hydroboration of  carbonyl
            [2]   CROCHETT M P, TYROL C C, WONG A S, et al. Iron-catalyzed   derivatives, imines, and carbon dioxide[J]. ACS  Catalysis, 2015,
                 Suzuki-Miyaura cross-coupling reactions between alkyl halides and   5(6): 3238-3259.
                 unactivated arylboronic esters[J]. Organic Letters, 2018, 20(17):   [23]  PEREIRA S, SREBNIK M. A study of hydroboration of alkenes and
                                                                   alkynes with pinacolborane catalyzed by transition metals[J].
                 5233-5237.
                                                                   Tetrahedron Letters, 1996, 37(19): 3283-3286.
            [3]   GEIER S J, VOGRLS C M, WESTCOTT S A. Current developments
                                                               [24]  OHMURA T, YAMAMOTO Y, MIYAURA N. Rhodium- or iridium-
                 in the catalyzed hydroboration aeaction[C]//Symposium on Boron
                 Reagents in Synthesis/39th American-Chemical-Society  Northeast   catalyzed trans-hydroboration of terminal alkynes, giving (Z)-1-alkenylboron
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