钯催化邻-碳硼烷基吡啶卤化物交叉偶联合成邻-碳硼烷基联芳、氨基吡啶和炔基吡啶衍生物

doi:10.6023/cjoc202310018

有机化学 ›› 2024, Vol. 44 ›› Issue (5): 1568-1575.DOI: 10.6023/cjoc202310018 上一篇下一篇

研究论文

钯催化邻-碳硼烷基吡啶卤化物交叉偶联合成邻-碳硼烷基联芳、氨基吡啶和炔基吡啶衍生物

罗东红^a,†, 李平^a,†, 陈志才^b,†, 杨佳怡^a, 孙梦凡^a, 陆居有^a^,^*()

a 海南大学化学化工学院海口 570228
b 海南大学材料科学与工程学院南海海洋资源利用国家重点实验室海口 570228

收稿日期:2023-10-21 修回日期:2024-01-13 发布日期:2024-01-30
作者简介:
†共同第一作者
基金资助:
国家自然科学基金(22161015); 海南省自然科学基金(221RC448)

Pd-Catalyzed Cross-Coupling of o-Carboranyl Pyridyl Halides: Synthesis of o-Carboranyl Biaryls, Aminopyridines and Alkynylpyridine Derivatives

Donghong Luo^a,†, Ping Li^a,†, Zhicai Chen^b,†, Jiayi Yang^a, Mengfan Sun^a, Juyou Lu^a()

a School of Chemistry and Chemical Engineering, Hainan University, Haikou 570228
b State Key Laboratory of Marine Resource Utilization in South China Sea, College of Materials Science and Engineering, Hainan University, Haikou 570228

Received:2023-10-21 Revised:2024-01-13 Published:2024-01-30
Contact: *E-mail: lujy@hainanu.edu.cn
About author:
†These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22161015); Hainan Provincial Natural Science Foundation of China(221RC448)

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摘要/Abstract

发展了一种钯催化邻-碳硼烷基吡啶卤化物与(杂)芳基硼酸交叉偶联反应合成邻-碳硼烷基联芳衍生物的高效方法. 该方法具有条件温和、官能团兼容性好等特点. 此外, 通过Buchwald-Hartwig反应及Sonogashira反应分别合成了邻-碳硼烷基氨基吡啶和炔基吡啶类化合物. 该类杂环芳基碳硼烷衍生物在发光材料以及药物等领域具有应用潜力.

关键词: 碳硼烷, 碳硼烷基吡啶卤化物, 交叉偶联, 钯催化

The Suzuki cross-coupling reaction between readily available o-carboranyl-substituted pyridyl halides and (hete- ro)arylboronic acids under Pd catalysis has been developed, providing access to o-carboranyl biaryls in yields of 35%~92%. The transformations proceed under mild conditions and with high functional group tolerance using commercially available coupling partners. Furthermore, the Buchwald-Hartwig reaction and Sonogashira reaction of o-carboranyl pyridyl halides are reported as well, leading to the facile synthesis of o-carboranyl aminopyridines and alkynylpyridine derivatives, respectively. It is believed that these heteroarylated carborane derivatives may find applications in luminescent materials and drug discovery.

Key words: carborane, carboranyl pyridyl halides, cross coupling, palladium catalysis

引用此文

罗东红, 李平, 陈志才, 杨佳怡, 孙梦凡, 陆居有. 钯催化邻-碳硼烷基吡啶卤化物交叉偶联合成邻-碳硼烷基联芳、氨基吡啶和炔基吡啶衍生物[J]. 有机化学, 2024, 44(5): 1568-1575.

Donghong Luo, Ping Li, Zhicai Chen, Jiayi Yang, Mengfan Sun, Juyou Lu. Pd-Catalyzed Cross-Coupling of o-Carboranyl Pyridyl Halides: Synthesis of o-Carboranyl Biaryls, Aminopyridines and Alkynylpyridine Derivatives[J]. Chinese Journal of Organic Chemistry, 2024, 44(5): 1568-1575.

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图/表 8

Figure 1. Luminescent compounds bearing o-carboranyl biaryl scaffolds

Figure 2. Strategies for synthesis of o-carboranyl biaryls

Entry	Catalyst	Base	Solvent	Yield^b/%
1	Pd(OAc)₂	CsF	THF	35
2	Pd(dba)₂	CsF	THF	7
3	Pd(P^tBu₃)₂	CsF	THF	69
4	Pd(PPh₃)₄	CsF	THF	13
5	—	CsF	THF	0
6	Pd(P^tBu₃)₂	K₂CO₃	THF	27
7	Pd(P^tBu₃)₂	K₂HPO₄	THF	29
8	Pd(P^tBu₃)₂	Li₂CO₃	THF	32
9	Pd(P^tBu₃)₂	Cs₂CO₃	THF	36
10	Pd(P^tBu₃)₂	CsF	DCE	47
11	Pd(P^tBu₃)₂	CsF	Toluene	42
12	Pd(P^tBu₃)₂	CsF	1,4-Dioxane	44
13	Pd(P^tBu₃)₂	CsF	CH₃CN	45

Table 1. Optimization of reaction conditionsa

Table 2. Substrate scope for Suzuki coupling of 1aa,b

Table 3. Substrate scope for Suzuki coupling of 1ba,b

Table 4. Substrate scope for Buchwald-Hartwig couplinga,b

Scheme 1. Synthesis of o-carboranyl alkynylpyridine

Figure 3. UV/Vis absorption (in toluene) (a) and PL (in toluene, CHCl3, and tetrahydrofuran (THF)) spectra (b) of compound 3n

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钯催化邻-碳硼烷基吡啶卤化物交叉偶联合成邻-碳硼烷基联芳、氨基吡啶和炔基吡啶衍生物

Pd-Catalyzed Cross-Coupling of o-Carboranyl Pyridyl Halides: Synthesis of o-Carboranyl Biaryls, Aminopyridines and Alkynylpyridine Derivatives

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