One-Pot Synthesis of Symmetrical Diselenides via Nano-CuO Catalysis through Aryl Iodides with Se0

doi:10.6023/cjoc202411011

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (7): 2425-2434.DOI: 10.6023/cjoc202411011 Previous Articles Next Articles

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纳米氧化铜催化单质硒与芳基碘“一锅法”合成对称二硒化物

冯书晓^a^,^*(), 钟轩^a, 陈嘉豪^a, 张宗洛^a, 谷广娜^a, 王俊岭^a, 郭亚菲^a, 马军营^a, 张守仁^b^,^*()

^a 河南科技大学化学化工学院河南洛阳 471023
^b 黄河科技学院纳米功能材料研究所河南省纳米复合材料与应用重点实验室郑州 450006

收稿日期:2025-01-16 修回日期:2025-02-08 发布日期:2025-02-27
通讯作者: 冯书晓, 张守仁
基金资助:
河南省科技攻关基金(242102311203)

One-Pot Synthesis of Symmetrical Diselenides via Nano-CuO Catalysis through Aryl Iodides with Se⁰

Shuxiao Feng^a^,^*(), Xuan Zhong^a, Jiahao Chen^a, Zongluo Zhang^a, Guangna Gu^a, Junling Wang^a, Yafei Guo^a, Junying Ma^a, Shouren Zhang^b^,^*()

^a School of Chemistry & Chemical Engineering, Henan University of Science and Technology, Luoyang, Henan 471023
^b Henan Key Laboratory of Nanocomposites and Applications, Institute of Nanostructured Functional Materials, Huanghe Science and Technology College, Zhengzhou 450006

Received:2025-01-16 Revised:2025-02-08 Published:2025-02-27
Contact: Shuxiao Feng, Shouren Zhang
Supported by:
Henan Scientific and Technological Research Projects(242102311203)

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Abstract

Selenium-containing compounds have unique chemical, enzymatic and biological properties. In recent years, diselenides, as the precursors of highly reactive selenium species, have become a class of important molecules with obvious biological activities and wide chemical applications. The efficient conversion strategy of elemental selenium is an effective way for inorganic selenium to organic selenium. A general synthesis method of symmetrical diselenides from elemental selenium and aryl iodine catalyzed by nano-CuO is reported. The method is suitable for substituting products with different functional groups at ortho-, meta- and para-site. Moreover, this method has the characteristics of simple reaction method, mild reaction conditions, high yield, no production of sulfur based odor gases during the reaction process, recyclable and reusable selenium raw materials, and suitable for the preparation of hundreds of grams.

Key words: elemental selenium, nano-copper oxide, aryl iodide, selenium-containing compound, symmetrical diselenide

Cite this article

Shuxiao Feng, Xuan Zhong, Jiahao Chen, Zongluo Zhang, Guangna Gu, Junling Wang, Yafei Guo, Junying Ma, Shouren Zhang. One-Pot Synthesis of Symmetrical Diselenides via Nano-CuO Catalysis through Aryl Iodides with Se⁰[J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2425-2434.

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Fig. & Tab. 11

References 23

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Entry	Cu catalyst	Solvent	Base	Temp./℃	Yield^b/%
1	Cu	DMF	NaOH	90	0
2	CuCl	DMF	NaOH	90	0
3	CuBr	DMF	NaOH	90	0
4	CuI	DMF	NaOH	90	0
5	Cu₂O	DMF	NaOH	90	0
6	CuO	DMF	NaOH	90	6
7	Cu₂Se	DMF	NaOH	90	4
8	Nano CuO	DMF	NaOH	90	10
9	Nano CuO	DMF	NaOH	120	37
10	Nano CuO	DMSO	NaOH	120	61
11	Nano CuO	Toluene	NaOH	Reflux	18
12	Nano CuO	ETOH	NaOH	Reflux	0
13	Nano CuO	THF	NaOH	Reflux	0
14	Nano CuO	H₂O	NaOH	Reflux	0
15	Nano CuO	CH₃CN	NaOH	Reflux	17
16	Nano CuO	DMSO	KOH	120	67
17	Nano CuO	DMSO	K₂CO₃	120	15
18	Nano CuO	DMSO	KBH₄	120	45
19	Nano CuO	DMSO	NH₃•H₂O	120	0

Entry	Cu catalyst	Solvent	Base	Temp./℃	Yield^b/%
1	Cu	DMF	NaOH	90	0
2	CuCl	DMF	NaOH	90	0
3	CuBr	DMF	NaOH	90	0
4	CuI	DMF	NaOH	90	0
5	Cu₂O	DMF	NaOH	90	0
6	CuO	DMF	NaOH	90	6
7	Cu₂Se	DMF	NaOH	90	4
8	Nano CuO	DMF	NaOH	90	10
9	Nano CuO	DMF	NaOH	120	37
10	Nano CuO	DMSO	NaOH	120	61
11	Nano CuO	Toluene	NaOH	Reflux	18
12	Nano CuO	ETOH	NaOH	Reflux	0
13	Nano CuO	THF	NaOH	Reflux	0
14	Nano CuO	H₂O	NaOH	Reflux	0
15	Nano CuO	CH₃CN	NaOH	Reflux	17
16	Nano CuO	DMSO	KOH	120	67
17	Nano CuO	DMSO	K₂CO₃	120	15
18	Nano CuO	DMSO	KBH₄	120	45
19	Nano CuO	DMSO	NH₃•H₂O	120	0

Entry	Nano-CuO/mol%	Se/equiv.	KOH/equiv.	t/h	Yield^b/%^b
1	15	2.00	2.00	1	52
2	15	2.00	2.00	2	67
3	15	2.00	2.00	3	86
4	15	2.00	2.00	4	86
5	15	2.00	2.00	5	85
6	15	1.00	2.00	3	18
7	15	1.25	2.00	3	34
8	15	2.50	2.00	3	86
9	15	3.00	2.00	3	85
10	15	2.00	1.00	3	46
11	15	2.00	2.25	3	93
12	15	2.00	2.75	3	54
13	15	2.00	3.00	3	50
14	3	2.00	2.25	3	90
15	5	2.00	2.25	3	92
16	10	2.00	2.25	3	92
17	20	2.00	2.25	3	94
18	30	2.00	2.25	3	93

Entry	Nano-CuO/mol%	Se/equiv.	KOH/equiv.	t/h	Yield^b/%^b
1	15	2.00	2.00	1	52
2	15	2.00	2.00	2	67
3	15	2.00	2.00	3	86
4	15	2.00	2.00	4	86
5	15	2.00	2.00	5	85
6	15	1.00	2.00	3	18
7	15	1.25	2.00	3	34
8	15	2.50	2.00	3	86
9	15	3.00	2.00	3	85
10	15	2.00	1.00	3	46
11	15	2.00	2.25	3	93
12	15	2.00	2.75	3	54
13	15	2.00	3.00	3	50
14	3	2.00	2.25	3	90
15	5	2.00	2.25	3	92
16	10	2.00	2.25	3	92
17	20	2.00	2.25	3	94
18	30	2.00	2.25	3	93

Entry	Substrate	Product	Yield^b/%	Entry	Substrate	Product	Yield^b/%
1	1a	2a	94	12	1l	2l	93
2	1b	2b	87	13	1m	2m	88
3	1c	2c	77	14	1n	2n	75
4	1d	2d	85	15	1o	2o	80
5	1e	2e	87	16	1p	2p	76
6	1f	2c	77	17	1q	2q	54
7	1g	2g	64	18	1r	2r	45
8	1h	2h	72	19	1s	2s	75
9	1i	2i	75	20	1t	2t	74
10	1j	2j	63	21	1u	2u	79
11	1k	2k	84	22	1v	2v	65

纳米氧化铜催化单质硒与芳基碘“一锅法”合成对称二硒化物

One-Pot Synthesis of Symmetrical Diselenides via Nano-CuO Catalysis through Aryl Iodides with Se⁰

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Fig. & Tab. 11

References 23

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Entry	Substrate	Product	Yield^b/%	Entry	Substrate	Product	Yield^b/%
1	1a	2a	94	12	1l	2l	93
2	1b	2b	87	13	1m	2m	88
3	1c	2c	77	14	1n	2n	75
4	1d	2d	85	15	1o	2o	80
5	1e	2e	87	16	1p	2p	76
6	1f	2c	77	17	1q	2q	54
7	1g	2g	64	18	1r	2r	45
8	1h	2h	72	19	1s	2s	75
9	1i	2i	75	20	1t	2t	74
10	1j	2j	63	21	1u	2u	79
11	1k	2k	84	22	1v	2v	65

Entry	Substrate	Product	Yield^b/%	Entry	Substrate	Product	Yield^b/%
1	1a	2a	94	12	1l	2l	93
2	1b	2b	87	13	1m	2m	88
3	1c	2c	77	14	1n	2n	75
4	1d	2d	85	15	1o	2o	80
5	1e	2e	87	16	1p	2p	76
6	1f	2c	77	17	1q	2q	54
7	1g	2g	64	18	1r	2r	45
8	1h	2h	72	19	1s	2s	75
9	1i	2i	75	20	1t	2t	74
10	1j	2j	63	21	1u	2u	79
11	1k	2k	84	22	1v	2v	65

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[3]	Qi Haitang, Song Guanglin, Quan Zhengjun, Wang Xicun. CuSO₄·5H₂O/NaAsc-Catalyzed Sonogashira Coupling Reaction of Aryl Iodides and Terminal Alkynes [J]. Chin. J. Org. Chem., 2017, 37(7): 1855-1859.
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[6]	Tang Jinpeng, Tang Yu, Yang Jun, Zhang Yuanming. Selenium-Promoted Homocoupling of Grignard Reagents [J]. Chin. J. Org. Chem., 2013, 33(05): 1010-1014.
[7]	ZHANG Guo-Beng, LI Pin-Hua. Pd(OAc)2 Catalyzed Sonogashira Cross-Coupling Reaction under Ultrasound Irradiation [J]. Chin. J. Org. Chem., 2010, 30(01): 117-119.

Entry	Se powder/g	Recycling selenium/g	Yield^b/%
1	6.36	3.14	91
2	3.14	1.55	76
3	1.55	0.81	62
4	0.80	0.43	56
5	0.43	0.43	0

Entry	Se powder/g	Recycling selenium/g	Yield^b/%
1	6.36	3.14	91
2	3.14	1.55	76
3	1.55	0.81	62
4	0.80	0.43	56
5	0.43	0.43	0

Entry	Substrate	Product	Yield^b/%	Entry	Substrate	Product	Yield^b/%
1	1a	2a	94	12	1l	2l	93
2	1b	2b	87	13	1m	2m	88
3	1c	2c	77	14	1n	2n	75
4	1d	2d	85	15	1o	2o	80
5	1e	2e	87	16	1p	2p	76
6	1f	2c	77	17	1q	2q	54
7	1g	2g	64	18	1r	2r	45
8	1h	2h	72	19	1s	2s	75
9	1i	2i	75	20	1t	2t	74
10	1j	2j	63	21	1u	2u	79
11	1k	2k	84	22	1v	2v	65

Entry	Substrate	Product	Yield^b/%	Entry	Substrate	Product	Yield^b/%
1	1a	2a	94	12	1l	2l	93
2	1b	2b	87	13	1m	2m	88
3	1c	2c	77	14	1n	2n	75
4	1d	2d	85	15	1o	2o	80
5	1e	2e	87	16	1p	2p	76
6	1f	2c	77	17	1q	2q	54
7	1g	2g	64	18	1r	2r	45
8	1h	2h	72	19	1s	2s	75
9	1i	2i	75	20	1t	2t	74
10	1j	2j	63	21	1u	2u	79
11	1k	2k	84	22	1v	2v	65

Entry	Substrate	Product	Yield^b/%	Entry	Substrate	Product	Yield^b/%
1	1a	2a	94	12	1l	2l	93
2	1b	2b	87	13	1m	2m	88
3	1c	2c	77	14	1n	2n	75
4	1d	2d	85	15	1o	2o	80
5	1e	2e	87	16	1p	2p	76
6	1f	2c	77	17	1q	2q	54
7	1g	2g	64	18	1r	2r	45
8	1h	2h	72	19	1s	2s	75
9	1i	2i	75	20	1t	2t	74
10	1j	2j	63	21	1u	2u	79
11	1k	2k	84	22	1v	2v	65

Entry	Substrate	Product	Yield^b/%	Entry	Substrate	Product	Yield^b/%
1	1a	2a	94	12	1l	2l	93
2	1b	2b	87	13	1m	2m	88
3	1c	2c	77	14	1n	2n	75
4	1d	2d	85	15	1o	2o	80
5	1e	2e	87	16	1p	2p	76
6	1f	2c	77	17	1q	2q	54
7	1g	2g	64	18	1r	2r	45
8	1h	2h	72	19	1s	2s	75
9	1i	2i	75	20	1t	2t	74
10	1j	2j	63	21	1u	2u	79
11	1k	2k	84	22	1v	2v	65