Page 66 - 《精细化工》2023年第5期
P. 66
·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