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

doi:10.6023/cjoc202211038

Abstract

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

Cite this article

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

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