Transition-Metal Free Radical-Mediated C—H Bond Alkynylation and Allylation of Ethers, Aldehydes and Amides

doi:10.6023/cjoc202207014

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (12): 4340-4349.DOI: 10.6023/cjoc202207014 Previous Articles Next Articles

Special Issue: 自由基化学专辑

ARTICLES

无过渡金属参与的醚、醛和酰胺C—H键自由基炔基化和烯丙基化反应

许耀辉^a, 吴镇^a, 吴新鑫^a, 朱晨^a^,^b^,^*()

a 苏州大学材料与化学化工学部江苏苏州 215123
b 中国科学院上海有机化学研究所天然产物有机合成重点实验室上海 200032

收稿日期:2022-07-06 修回日期:2022-08-14 发布日期:2022-09-01
通讯作者: 朱晨
作者简介:
^†共同第一作者
基金资助:
国家自然科学基金(21971173); 国家自然科学基金(22171201)

Transition-Metal Free Radical-Mediated C—H Bond Alkynylation and Allylation of Ethers, Aldehydes and Amides

Yaohui Xu^a, Zhen Wu^a, Xinxin Wu^a, Chen Zhu^a^,^b()

a College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123
b Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2022-07-06 Revised:2022-08-14 Published:2022-09-01
Contact: Chen Zhu
About author:
^†These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21971173); National Natural Science Foundation of China(22171201)

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Abstract

Ethers, aldehydes, and amides are widely found in natural products and pharmaceutical molecules, and employed as inexpensive materials in synthetic chemistry. Radical-mediated heteroatomic α-C—H bond functionalization provides an efficient strategy for structural modification of ethers, aldehydes, and amides. New approaches of C—H alkynylation and allylation through phenyliodine bis(trifluoroacetate) (PIFA) induced hydrogen atom transfer (HAT) under visible-light irradiation are reported. The method is operationally simple, leading to the corresponding alkynylated and allylated products in moderate to good yields. The protocol features mild and transition-metal free conditions, broad functional group compatibility, and is adapted to a diversity of ethers, aldehydes, and amides as well as various alkynylating and allylating reagents.

Key words: radical reaction, alkynylation, allylation, transition-metal free, C—H bond functionalization

Cite this article

Yaohui Xu, Zhen Wu, Xinxin Wu, Chen Zhu. Transition-Metal Free Radical-Mediated C—H Bond Alkynylation and Allylation of Ethers, Aldehydes and Amides[J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4340-4349.

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Entry	PIFA/ equiv.	THF/mL	K₂CO₃/ equiv.	Solvent	Yield/%
1^b	1.5	—	1.5	MeCN	36
2^b	1.5	—	1.5	PhCF₃	21
3^b	1.5	—	1.5	DCM	14
4^b	1.5	—	1.5	DCE	14
5^b	1.5	—	1.5	DMSO	29
6^b	1.5	—	1.5	Acetone	44
7^b	1.5	—	1.5	EtOAc	47
8^b^,^c	1.5	—	1.5	EtOAc	41
9^b^,^d	1.5	—	1.5	EtOAc	28
10	1.5	2	1.5	—	68
11^e	1.5	2	1.5	—	65
12	1.5	2	—	—	19
13	1.5	1	1.5	—	54
14	1.5	5	1.5	—	78
15	1.5	10	1.5	—	78
16^e	1.5	10	1.5	—	66
17^e	2	10	2	—	76
18^e	2	5	2	—	77

Entry	PIFA/ equiv.	THF/mL	K₂CO₃/ equiv.	Solvent	Yield/%
1^b	1.5	—	1.5	MeCN	36
2^b	1.5	—	1.5	PhCF₃	21
3^b	1.5	—	1.5	DCM	14
4^b	1.5	—	1.5	DCE	14
5^b	1.5	—	1.5	DMSO	29
6^b	1.5	—	1.5	Acetone	44
7^b	1.5	—	1.5	EtOAc	47
8^b^,^c	1.5	—	1.5	EtOAc	41
9^b^,^d	1.5	—	1.5	EtOAc	28
10	1.5	2	1.5	—	68
11^e	1.5	2	1.5	—	65
12	1.5	2	—	—	19
13	1.5	1	1.5	—	54
14	1.5	5	1.5	—	78
15	1.5	10	1.5	—	78
16^e	1.5	10	1.5	—	66
17^e	2	10	2	—	76
18^e	2	5	2	—	77

无过渡金属参与的醚、醛和酰胺C—H键自由基炔基化和烯丙基化反应

Transition-Metal Free Radical-Mediated C—H Bond Alkynylation and Allylation of Ethers, Aldehydes and Amides

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