Sodiump-Toluenesulfinate/KI-Mediated Aerobic Oxidative Iodination of Terminal Alkynes for Synthesis of 1-Iodoalkynes and 1,3-Diynes

doi:10.6023/cjoc202007031

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (1): 394-399.DOI: 10.6023/cjoc202007031 Previous Articles Next Articles

Article

对甲苯亚磺酸钠/KI介导端炔的需氧氧化碘代反应合成1-碘代炔和1,3-二炔

周鹏^a^,^*(), 冯尚伟^a, 邱会华^a, 张建涛^a^,^*()

a 广东石油化工学院化学学院广东茂名 525000

收稿日期:2020-07-09 修回日期:2020-09-11 发布日期:2020-10-12
通讯作者: 周鹏, 张建涛
作者简介:
* Corresponding author. E-mail: zzd83@aliyun.com; 1351248781@qq.com
基金资助:
国家自然科学基金(21602035); 广东省自然科学基金(2016A030307030); 广东石油化工学院创新研究团队(519124)

Sodiump-Toluenesulfinate/KI-Mediated Aerobic Oxidative Iodination of Terminal Alkynes for Synthesis of 1-Iodoalkynes and 1,3-Diynes

Peng Zhou^a^,^*(), Shangwei Feng^a, Huihua Qiu^a, Jiantao Zhang^a^,^*()

a College of Chemistry, Guangdong University of Petrochemical Technology, Maoming, Guangdong 525000

Received:2020-07-09 Revised:2020-09-11 Published:2020-10-12
Contact: Peng Zhou, Jiantao Zhang
Supported by:
the National Natural Science Foundation of China(21602035); the Natural Science Foundation of Guangdong Province(2016A030307030); the Program for Innovative Research Team of Guangdong University of Petrochemical Technology(519124)

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Abstract

A practical and environmentally friendly protocol for the synthesis of 1-iodoalkynes was developed via sodium sulfinate-KI mediated aerobic oxidative iodination of terminal alkynes. This transformation features simple operation, high efficiency, broad functional-group tolerance and mild reaction conditions. Especially, dioxygen was used in these reactions which avoided the addition of hazardous or toxic oxidants. Moreover, for the purpose of increasing the synthetic utility of this method, an efficient transition-metal-free synthetic approach to symmetrical 1,3-diynes was developed via the iodination/ homocoupling of terminal alkynes in a one-pot manner.

Key words: terminal alkyne, 1-iodoalkyne, air, sodium sulfinate, 1,3-diyne

Cite this article

Peng Zhou, Shangwei Feng, Huihua Qiu, Jiantao Zhang. Sodiump-Toluenesulfinate/KI-Mediated Aerobic Oxidative Iodination of Terminal Alkynes for Synthesis of 1-Iodoalkynes and 1,3-Diynes[J]. Chinese Journal of Organic Chemistry, 2021, 41(1): 394-399.

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Entry	Iodide salt	n(TolSO ₂Na)/mmol	Solvent	Yield ^b /%
1 ^c	KI	—	CH ₃OH	NR
2	KI	0.5	CH ₃OH	67
3	KI	0.6	CH ₃OH	80
4	KI	0.75	CH ₃OH	89
5	KI	0.85	CH ₃OH	88
6	NaI	0.75	CH ₃OH	85
7	ZnI ₂	0.75	CH ₃OH	68
8	NH ₄I	0.75	CH ₃OH	64
9	KI	0.75	C ₂ H ₅ OH	93
10	KI	0.75	CH ₃CN	87
11	KI	0.75	CH ₂Cl ₂	84
12	KI	0.75	p-Xylene	83
13	KI	0.75	DMF	Trace
14	KI	0.75	DMSO	Trace
15	KI	0.75	H ₂O	Trace
16 ^d	KI	0.75	C ₂H ₅OH	Trace

Entry	Iodide salt	n(TolSO ₂Na)/mmol	Solvent	Yield ^b /%
1 ^c	KI	—	CH ₃OH	NR
2	KI	0.5	CH ₃OH	67
3	KI	0.6	CH ₃OH	80
4	KI	0.75	CH ₃OH	89
5	KI	0.85	CH ₃OH	88
6	NaI	0.75	CH ₃OH	85
7	ZnI ₂	0.75	CH ₃OH	68
8	NH ₄I	0.75	CH ₃OH	64
9	KI	0.75	C ₂ H ₅ OH	93
10	KI	0.75	CH ₃CN	87
11	KI	0.75	CH ₂Cl ₂	84
12	KI	0.75	p-Xylene	83
13	KI	0.75	DMF	Trace
14	KI	0.75	DMSO	Trace
15	KI	0.75	H ₂O	Trace
16 ^d	KI	0.75	C ₂H ₅OH	Trace

对甲苯亚磺酸钠/KI介导端炔的需氧氧化碘代反应合成1-碘代炔和1,3-二炔

Sodiump-Toluenesulfinate/KI-Mediated Aerobic Oxidative Iodination of Terminal Alkynes for Synthesis of 1-Iodoalkynes and 1,3-Diynes

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