酰胺功能化吡啶/嘧啶螯合氮杂环卡宾钯化合物的合成、结构及其催化的咪唑C-5芳基化反应

doi:10.6023/cjoc202206005

摘要/Abstract

以氨基酸为原料, 合成了一系列N-烷基酰胺-N'-吡啶/嘧啶双官能团化的咪唑鎓盐, 室温下与Pd(OAc)₂在CH₂Cl₂溶液中经直接金属化反应生成吡啶/嘧啶螯合的氮杂环卡宾钯化合物. 所得化合物的结构经核磁共振(NMR)、质谱(MS)或元素分析(EA)鉴定, 其中吡啶螯合氮杂环卡宾钯化合物5c的结构进一步经X射线单晶衍射确证. 催化活性研究表明, 使用二甲基乙酰胺(DMAc)为溶剂、KOAc为碱时, 这些化合物对咪唑衍生物的C-5芳基化反应表现出很高的催化活性.

关键词: 氮杂环卡宾, 螯合, 钯化合物, 咪唑芳基化反应

A series of N-alkylamide-N'-pyridine/pyrimidine di-functionalized imidazolium salts were synthesized using amino acids as starting material. The following direction metallation with Pd(OAc)₂ in CH₂Cl₂ at room temperature produced chelating N-heterocyclic carbene (NHC) palladium complexes with pyridine/pyrimidine coordinated. The structures have been characterized by nuclear magnetic resonance (NMR), mass spectrum (MS) or elemental analysis (EA). The molecular strucuture of pyridine chelating NHC palladium complex 5c has been further characterized unambiguously by X-ray single crystal analysis. Catalytic activity exploration of the complexes demonstrated their high efficiency towards the C-5 arylation of imidazole derivatives in dimethylacetamide (DMAc) with KOAc as base.

Key words: N-heterocyclic carbene, chelating, palladium complex, arylation of imidazoles

引用此文

孟祥辉, 杨亮茹, 刘琪琳, 董振华, 袁金伟, 肖咏梅, 毛璞. 酰胺功能化吡啶/嘧啶螯合氮杂环卡宾钯化合物的合成、结构及其催化的咪唑C-5芳基化反应[J]. 有机化学, 2022, 42(11): 3747-3756.

Xianghui Meng, Liangru Yang, Qilin Liu, Zhenhua Dong, Jinwei Yuan, Yongmei Xiao, Pu Mao. Amide Functionalized Pyridine/Pyrimidine Chelating N-Heterocyclic Carbene Palladium Complexes: Synthesis, Structure, and Catalysis for C-5 Arylation of Imidazoles[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3747-3756.

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Entry^a	NHC-Pd (mol%)	Yield^b/%
1	5a (2.0)	65
2	5b (2.0)	79
3	5c (2.0)	74
4	5d (2.0)	81
5	5e (2.0)	76
6	5f (2.0)	99
7	5f (1.0)	87
8	C1 (2.0)	55
9	C2 (2.0)	67
10	C3 (2.0)	57
11	C4 (2.0)	89

Entry^a	NHC-Pd (mol%)	Yield^b/%
1	5a (2.0)	65
2	5b (2.0)	79
3	5c (2.0)	74
4	5d (2.0)	81
5	5e (2.0)	76
6	5f (2.0)	99
7	5f (1.0)	87
8	C1 (2.0)	55
9	C2 (2.0)	67
10	C3 (2.0)	57
11	C4 (2.0)	89

Entry ^a	Imidazole	Bromide	Yield^b/%
1	1,2-Dimethylimidazole	p-BrC₆H₄COCH₃	99
2	1,2-Dimethylimidazole	m-BrC₆H₄COCH₃	83
3	1,2-Dimethylimidazole	o-BrC₆H₄COCH₃	0
4	1,2-Dimethylimidazole	p-BrC₆H₄CHO	99
5	1,2-Dimethylimidazole	m-BrC₆H₄CHO	84
6	1,2-Dimethylimidazole	o-BrC₆H₄CHO	70
7	1,2-Dimethylimidazole	p-BrC₆H₄CN	96
8	1,2-Dimethylimidazole	p-BrC₆H₄CH₂CN	74
9	1,2-Dimethylimidazole	p-BrC₆H₄CF₃	91
10	1,2-Dimethylimidazole	p-BrC₆H₄F	90
11	1,2-Dimethylimidazole	C₆H₅Br	66
12	1,2-Dimethylimidazole	p-BrC₆H₄CH₃	54
13	1,2-Dimethylimidazole	m-BrC₆H₄CH₃	51
14	1,2-Dimethylimidazole	o-BrC₆H₄CH₃	0
15	1,2-Dimethylimidazole	p-BrC₆H₄OCH₃	49
16	1,2-Dimethylimidazole	m-BrC₆H₄OCH₃	56
17	1,2-Dimethylimidazole	o-BrC₆H₄OCH₃	0
18	1-Methylimidazole	p-BrC₆H₄COCH₃	92
19	1-Methylimidazole	p-BrC₆H₄CHO	81
21	1-Methylimidazole	m-BrC₆H₄CHO	70
22	1-Methylimidazole	o-BrC₆H₄CHO	46

Entry ^a	Imidazole	Bromide	Yield^b/%
1	1,2-Dimethylimidazole	p-BrC₆H₄COCH₃	99
2	1,2-Dimethylimidazole	m-BrC₆H₄COCH₃	83
3	1,2-Dimethylimidazole	o-BrC₆H₄COCH₃	0
4	1,2-Dimethylimidazole	p-BrC₆H₄CHO	99
5	1,2-Dimethylimidazole	m-BrC₆H₄CHO	84
6	1,2-Dimethylimidazole	o-BrC₆H₄CHO	70
7	1,2-Dimethylimidazole	p-BrC₆H₄CN	96
8	1,2-Dimethylimidazole	p-BrC₆H₄CH₂CN	74
9	1,2-Dimethylimidazole	p-BrC₆H₄CF₃	91
10	1,2-Dimethylimidazole	p-BrC₆H₄F	90
11	1,2-Dimethylimidazole	C₆H₅Br	66
12	1,2-Dimethylimidazole	p-BrC₆H₄CH₃	54
13	1,2-Dimethylimidazole	m-BrC₆H₄CH₃	51
14	1,2-Dimethylimidazole	o-BrC₆H₄CH₃	0
15	1,2-Dimethylimidazole	p-BrC₆H₄OCH₃	49
16	1,2-Dimethylimidazole	m-BrC₆H₄OCH₃	56
17	1,2-Dimethylimidazole	o-BrC₆H₄OCH₃	0
18	1-Methylimidazole	p-BrC₆H₄COCH₃	92
19	1-Methylimidazole	p-BrC₆H₄CHO	81
21	1-Methylimidazole	m-BrC₆H₄CHO	70
22	1-Methylimidazole	o-BrC₆H₄CHO	46