含吡咯基配体的锌、锂和镁配合物的合成与表征及其对芳基碘代物的硼化反应和醛、酮的硼氢化反应的催化作用

doi:10.6023/cjoc202211038

摘要/Abstract

用ZnEt₂分别与两个含吡咯基的配体2-(2-((((1H-吡咯-2-基)亚甲基)氨基)甲基)-1H-吡咯-1-基)-N,N-二甲基乙烷-1-胺(HL1)和N-((1H-吡咯-2-甲基)甲基)-1-(1H-吡啶-2-基)甲亚胺(H₂L2)反应, 合成了两个化合物[Zn(L1)Et] (1)和[Zn₂(L2)₂(THF)₂] (2). 通过核磁共振波谱、元素分析和单晶X射线衍射对配合物进行了表征. 研究了配合物1和2对芳基碘与B₂Pin₂ (B₂Pin₂=4,4,4',4',5,5,5',5'-八甲基-2,2′-双(1,3,2-二氧杂硼烷))偶联反应的催化作用. 它们都对这类硼化反应有催化活性. 化合物1显示出比2更高的活性. 化合物1催化的这类硼化反应具有温和的条件、宽的底物范围和较好的官能团相容性的特点. 此外, 还研究了先前报道的两种已知化合物[Li₂(L1)₂] (3)和[Mg(L1)₂(THF)₂] (4)对频哪硼烷(HBpin)和醛、酮的硼氢化反应的催化作用. 配合物3和4对该类反应具有较好的催化活性, 在很短的时间内以优异的产率生成了一系列硼酸酯.

关键词: 硼化反应, 硼氢化反应, 锌化合物, 催化

The reactions of ZnEt₂ with two pyrrolyl ligands 2-(2-((((1H-pyrrol-2-yl)methylene)amino)methyl)-1H-pyrrol-1- yl)-N,N-dimethylethan-1-amine (HL1) and N-((1H-pyrrol-2-yl)methyl)-1-(1H-pyrrol-2-yl)methanimine (H₂L2) generated a zinc ethyl compound [Zn(L1)Et] (1) and a dinuclear complex [Zn₂(L2)₂(THF)₂] (2). The complexes were characterized by ¹H NMR, ¹³C NMR, elemental analysis, and single-crystal X-ray diffraction. Complexes 1 and 2 were employed as catalysts for the borylation of aryl iodides with B₂Pin₂ (B₂Pin₂=4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane)). They were both active for this coupling reaction. Complex 1 displays higher activity than that of 2. This borylation transformation promoted by 1 features mild condition, wide substrate scope and high functional group compatibility. Moreover, the catalytic activities of two known compounds previously reported by our group, namely, [Li₂(L1)₂] (3) and [Mg(L1)₂(THF)₂] (4), toward borylation of aryl iodides with B₂Pin₂ were also explored. They cannot catalyze this coupling reaction. Nevertheless, complexes 3 and 4 were catalytically active toward hydroboration of aldehydes and ketones by pinacolborane (HBpin), giving a variety of borate esters in excellent yields in a very short time.

Key words: borylation, hydroboration, zinc complexes, catalysis

引用此文

党燕, 贾朝红, 王亚兰, 王丽, 李亚飞, 李亚红. 含吡咯基配体的锌、锂和镁配合物的合成与表征及其对芳基碘代物的硼化反应和醛、酮的硼氢化反应的催化作用[J]. 有机化学, 2023, 43(3): 1124-1135.

Yan Dang, Chaohong Jia, Yalan Wang, Li Wang, Yafei Li, Yahong Li. Synthesis and Characterization of Zinc, Lithium and Magnesium Complexes Containing Pyrrolyl Ligands, and Utilization as Catalysts in Borylation of Aryl Iodides and Hydroboration of Aldehydes and Ketones[J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1124-1135.

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Entry	Reactant	Time/h	Cat. (mol%)	Product	Yield/%
1		12	1 (5)		82^b
2		12	2 (10)		43^b
3		12	1 (10)		75^c
4		12	2 (10)		64^b
5		12	1 (10)		64^c
Entry	Reactant	Time/h	Cat. (mol%)	Product	Yield/%
6		12	2 (10)		83^b
7		12	1 (10)		89^c
8		12	2 (10)		65^b
9		12	1 (10)		71^c
10		12	2 (10)		44^b
11		12	1 (5)		99^b
12		12	2 (10)		71^b
13		12	1 (5)	—	NP
14		12	2 (10)	—	NP
15		12	1 (10)		63^c
16		12	1 (10)		75^c
Entry	Reactant	Time/h	Cat. (mol%)	Product	Yield/%
17		12	1 (10)		41^b
18		12	1 (10)		39^c
19		12	1 (10)	—	NP^d
20		12	1 (10)	—	NP^d

Entry	Reactant	Time/h	Cat. (mol%)	Product	Yield/%
1		12	1 (5)		82^b
2		12	2 (10)		43^b
3		12	1 (10)		75^c
4		12	2 (10)		64^b
5		12	1 (10)		64^c
Entry	Reactant	Time/h	Cat. (mol%)	Product	Yield/%
6		12	2 (10)		83^b
7		12	1 (10)		89^c
8		12	2 (10)		65^b
9		12	1 (10)		71^c
10		12	2 (10)		44^b
11		12	1 (5)		99^b
12		12	2 (10)		71^b
13		12	1 (5)	—	NP
14		12	2 (10)	—	NP
15		12	1 (10)		63^c
16		12	1 (10)		75^c
Entry	Reactant	Time/h	Cat. (mol%)	Product	Yield/%
17		12	1 (10)		41^b
18		12	1 (10)		39^c
19		12	1 (10)	—	NP^d
20		12	1 (10)	—	NP^d

Entry	Reactant	Time/min	Cat.	Product	Yield^b/%
1		30	3		>99
2		30	4		>99
3		30	3		—
4		30	4		>99
5		30	3		>99
6		30	4		64
7		30	3		>99
Entry	Reactant	Time/min	Cat.	Product	Yield^b/%
8		30	4		>99
9		30	3		>99
10		30	4		>99

Entry	Reactant	Time/min	Cat.	Product	Yield^b/%
1		30	3		>99
2		30	4		>99
3		30	3		—
4		30	4		>99
5		30	3		>99
6		30	4		64
7		30	3		>99
Entry	Reactant	Time/min	Cat.	Product	Yield^b/%
8		30	4		>99
9		30	3		>99
10		30	4		>99

Entry	Reactant	Time/min	Cat.	Product	Yield^b/%
1		30	3		>99
2		30	4		>99
3		30	3		>99
4		30	4		>99
5		30	3		>99
6		30	4		>99
Entry	Reactant	Time/min	Cat.	Product	Yield^b/%
7		30	3		>99
8		30	4		>99
9		30	3		>99
10		30	4		>99