Page 79 - 《精细化工》2021年第11期

第 11 期 黄剑辉，等: 非平面芳烃的碳氢活化研究进展
羧基，发生 C—H 键活化反应生成新颖的富勒烯菲
类衍生物Ⅴg，产率 19%~46%。
通过 C—H 键活化策略，富勒烯 C 60 还可与芳基
磺酸、2-苯乙基/苄醇、仲烷基芳基酮、苯酚、芳酰
基化合物、4-羟基香豆素、肟等化合物反应
得到一系列富勒烯 C 60 稠合的中等（五元环~七元环）
芳杂环衍生物，极大丰富了富勒烯衍生物的种类。
随着人们对其不断研究，C 60 及其衍生物在电化学、
生物医药科学、材料等领域展现出广阔的应用前景。
4 总结与展望
本文总结了典型的非平面芳烃——环仿、螺烯、
碗烯、花烯以及富勒烯 C 60 的 C—H 活化反应。C—
H 键的反应选择性和反应活性是相关研究的关键，
导向基团的存在、配体的选择以及过渡金属催化剂
的使用对 C—H 键的活化都有着极其重要的作用。
非平面芳烃具有独特的物理、化学性质，在医
药、电化学、催化、新型材料中已展现出广阔的应
用前景。C—H 活化策略的应用可以加快非平面芳烃
的多样化衍生,使快速构建结构复杂、功能多样的非
平面芳烃成为可能。然而，非平面芳烃的 C—H 活
化仍面临着许多挑战：非平面芳烃由于合成路线长、
总产率不高等不足，使其暂时不能大规模应用于工
业化生产；已有的非平面芳烃的结构类型和数量还
较少，远远不能满足人们进行应用研究的需要；反应
的区域选择性、位置及导向基团特异性仍需探索。
因此，发展更加高效、可循环利用的催化体系
是 C—H 键活化的重要任务。目前非平面芳烃的研
究取得了一定的成果，但仍有许多 C—H 活化策略
未被研究。相信未来定能优化非平面芳烃的合成路
线，寻找高效、环境友好的催化体系，降低现有催
化剂的合成成本，从而使 C—H 活化策略能真正运
用到工业化生产中，获得更多优秀的非平面芳烃，
为非平面芳烃应用到实际生活中提供可能。
参考文献：
[1] NESTOROS E, STUPARU M C. Corannulene: A molecular bowl of
carbon with multifaceted properties and diverse applications[J].
Chemical Communications, 2018, 54(50): 6503-6519.
·2225·
[2] HASSAN Z, SPULING E, KNOLL D M, et al. Regioselective
functionalization of [2.2]paracyclophanes: Recent synthetic progress
and perspectives[J]. Angewandte Chemie International Edition, 2020,
59(6): 2156-2170.
[3] SUN C L, LI H, YU D G, et al. An efficient organocatalytic method
for constructing biaryls through aromatic C—H activation[J]. Nature
Chemistry, 2010, 2(12): 1044-1049.
[4] KUHL N, HOPKINSON M N, WENCEL-DELORD J, et al. Beyond
directing groups: Transition-metal-catalyzed C—H activation of
simple arenes[J]. Angewandte Chemie International Edition, 2012,
51(41): 10236-10254.
[5] SONG G, WANG F, LI X. C—C, C—O and C—N bond formation
via rhodium(Ⅲ)-catalyzed oxidative C—H activation[J]. Chemical
Society Reviews, 2012, 41(9): 3651-3678.
[6] WANG P, VERMA P, XIA G, et al. Ligand-accelerated non-directed
C — H functionalization of arenes[J]. Nature, 2017, 551(7681):
489-493.
[69-75] ， [7] BROWN C J, FARTHING A C. Preparation and structure of
di-p-xylylene[J]. Nature, 1949, 164(4178): 915-916.
[8] CRAM D J, STEINBERG H. Macro rings. ⅠPreparation and
spectra of the paracyclophanes[J]. Journal of the American Chemical
Society, 1951, 73(12): 5691-5704.
[9] PYE P J, ROSSEN K, REAMER R A, et al. [2.2]Phanephos-ruthenium(Ⅱ)
complexes: Highly active asymmetric catalysts for the hydrogenation
of β-ketoesters[J]. Tetrahedron Letters, 1998, 39(25): 4441-4444.
[10] DOMINGUEZ B, ZANOTTI-GEROSA A, HEMS W. Electrophilic
substitution of dibromoparacyclophane: A route to novel paracyclophane
phosphine ligands[J]. Organic Letters, 2004, 6(12): 1927-1930.
[11] CRAM D J, ALLINGER N L. Macro rings. Ⅻ Stereochemical
consequences of steric compression in the smallest paracyclophane1[J].
Journal of the American Chemical Society, 1955, 77(23): 6289-6294.
[12] BANFI S, MANFREDI A, MONTANARI F, et al. Synthesis of
chiral Mn(Ⅲ)-meso-tetrakis-[2.2]-p-cyclophanyl-porphyrin: A new
catalyst for enantioselective epoxidation[J]. Journal of Molecular
Catalysis A: Chemical, 1996, 113(1): 77-86.
[13] BARTHOLOMEW G P, BAZAN G C. Synthesis, characterization,
and spectroscopy of 4,7,12,15-[2.2]paracyclophane containing donor
and acceptor groups: Impact of substitution patterns on through-space
charge transfer[J]. Journal of the American Chemical Society, 2002,
124(18): 5183-5196.
[14] HASEGAWA M, KOBAYAKAWA K, NOJIMA Y, et al. Synthesis
and chiroptical properties of stereogenic cyclic dimers based on
2,2′-biselenophene and [2.2]paracyclophane[J]. Organic & Biomolecular
Chemistry, 2019, 17(39): 8822-8826.
[15] LENNARTZ P, RAABE G, BOLM C. Palladium-catalyzed C—H
bond acetoxylation: An approach to ortho-substituted
hydroxy[2.2]paracyclophane derivatives[J]. Advanced Synthesis &
Catalysis, 2012, 354(17): 3237-3249.
[16] STOWERS K J, SANFORD M S. Mechanistic comparison between
Pd-catalyzed ligand-directed C—H chlorination and C—H acetoxylation[J].
Organic Letters, 2009, 11(20): 4584-4587.
[17] KRAMER J J P, YILDIZ C, NIEGER M, et al. Direct access to
4,5-disubstituted [2.2]paracyclophanes by selective ortho-halogenation
with Pd-catalyzed C—H activation[J]. European Journal of Organic
Chemistry, 2014, (6): 1287-1295.
[18] SCHAAL P, BAARS H, RAABE G, et al. Phenyliodine diacetate-
mediatedpara-functionalizations of amido- and amino-substituted
[2.2]paracyclophanes[J]. Advanced Synthesis & Catalysis, 2013,
355(13): 2506-2512.
[19] ZIPPEL C, SPULING E, HASSAN Z, et al. Controlling regioselectivity
in palladium-catalyzed C — H activation/aryl-aryl coupling of
4-phenylamino[2.2]paracyclophane[J]. Chemistry-A European Journal,
2020, 26(61): 13771-13775.
[20] LENNARTZ P, RAABE G, BOLM C. Synthesis of planar chiral