Visible-Light-Mediated O—H Functionalization Reactions of Alkenyl Alcohols with Diazo Compounds

doi:10.6023/cjoc202502001

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (8): 3004-3016.DOI: 10.6023/cjoc202502001 Previous Articles Next Articles

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可见光介导的烯醇和重氮化合物之间的O—H键官能团化反应

谢昊池, 秦永康, 杨婷, 李湖进, 孙佳嘉, 钱明成, 赵帅^*(), 侯亚男^*(), 陈新^*()

常州大学药学院江苏常州 213164

收稿日期:2025-02-02 修回日期:2025-02-21 发布日期:2025-03-13
基金资助:
国家自然科学基金(21602018); 国家自然科学基金(22077012)

Visible-Light-Mediated O—H Functionalization Reactions of Alkenyl Alcohols with Diazo Compounds

Haochi Xie, Yongkang Qin, Ting Yang, Hujin Li, Jiajia Sun, Mingcheng Qian, Shuai Zhao^*(), Ya'nan Hou^*(), Xin Chen^*()

School of Pharmacy, Changzhou University, Changzhou, Jiangsu 213164

Received:2025-02-02 Revised:2025-02-21 Published:2025-03-13
Contact: *E-mail:zhaoshuai@cczu.edu.cn;houyn@cczu.edu.cn;xinchen@cczu.edu.cn
Supported by:
National Natural Science Foundation of China(21602018); National Natural Science Foundation of China(22077012)

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Abstract

Visible-light-mediated O—H functionalization reactions of alcohols with diazo compounds have been fully developed in recent years. However, alkenyl and acetylenic alcohols were rarely examined in these reactions due to the inevitable side reactions involving cycloaddition. Herein, the visible-light-mediated O—H functionalization reactions of alkenyl alcohols with diazo compounds were developed. This process competed favorably with the cycloaddition reaction. A series of multifunctional ethers were provided in low to high yields with aryldiazoacetates or 3-diazooxindoles. Biologically relevant spirooxindole-fused oxacycle could be easily accessed from the O—H functionalization product of alkenyl alcohol and 3-diazooxindole.

Key words: visible-light, O—H functionalization, alkenyl alcohol, diazo compound, spirooxindole-fused oxacycle

Cite this article

Haochi Xie, Yongkang Qin, Ting Yang, Hujin Li, Jiajia Sun, Mingcheng Qian, Shuai Zhao, Ya'nan Hou, Xin Chen. Visible-Light-Mediated O—H Functionalization Reactions of Alkenyl Alcohols with Diazo Compounds[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 3004-3016.

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Fig. & Tab. 8

Scheme 1. Visible-light-mediated reactions of alcohols with diazo compounds

Entry	n(1a)∶n(2a)	c(1a)/(mol/L)	t/h	Yield^b/%
1	1∶1	0.1	16	27
2	1∶3	0.1	14	31
3	1∶5	0.1	12	42
4	1∶7	0.1	14	54
5	1∶10	0.1	17	64
6	1∶20	0.1	14	60
7	1∶10	0.05	11	46
8	1∶10	0.2	14	68
9	1∶10	0.4	15	73
10	1∶10	0.8	16	64
11	2a as solvent	—	11	56
12^c	1∶10	0.4	48	NR

Table 1. Optimization of reaction conditionsa

Table 2. Scope of aryldiazoacetates

Table 3. Scope of alkenyl alcoholsa

Table 4. Scope of the O—H functionalization reaction of 3-diazooxindole with alkenyl alcohola

Scheme 2. (a) Visible-light-mediated O—H functionalization reaction of cholesterol with aryldiazoacetate 1a, (b) synthesis of spirooxindole-fused oxacycle from 5a, and (c) epoxidation of 3a

Scheme 3. Radical trapping experiments

Scheme 4. Postulated mechanism of the O—H functionalization reaction

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可见光介导的烯醇和重氮化合物之间的O—H键官能团化反应

Visible-Light-Mediated O—H Functionalization Reactions of Alkenyl Alcohols with Diazo Compounds

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