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.