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

doi:10.6023/cjoc202502001

摘要/Abstract

近些年来, 可见光介导的醇和重氮化合物之间的O—H键官能团化反应已经发展成熟. 然而, 在这些已经报道的反应中, 烯醇和炔醇化合物很少被研究, 这主要是由于这两类化合物的反应通常伴有难以避免的副反应, 比如环加成反应. 开发了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, 此反应比环加成反应优先发生. 通过选用芳基重氮乙酸酯类和3-重氮氧吲哚类底物, 反应以低到高的产率合成了一系列多官能团的醚类化合物. 其中烯醇和3-重氮氧吲哚类底物的O—H键官能团化产物可以很容易地转化为有潜在重要生物活性的氧吲哚螺氧杂环类化合物.

关键词: 可见光, O—H键官能团化, 烯醇, 重氮化合物, 氧吲哚螺氧杂环

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

引用此文

谢昊池, 秦永康, 杨婷, 李湖进, 孙佳嘉, 钱明成, 赵帅, 侯亚男, 陈新. 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[J]. 有机化学, 2025, 45(8): 3004-3016.

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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图/表 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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