维生素B12催化的芳基烯烃硫氰化/肟化反应研究

doi:10.6023/cjoc202603016

有机化学 ›› 2026, Vol. 46 ›› Issue (10): 4098-4107.DOI: 10.6023/cjoc202603016 上一篇下一篇

研究论文

维生素B₁₂催化的芳基烯烃硫氰化/肟化反应研究

左子沂^a, 吕游^b^,^c, 黄艳萍^a, 刘晓强^b^,^*(), 钱宇^a^,^*(), 杨义^a^,^*()

^a 四川轻化工大学晨光高性能氟材料创新中心绿色催化四川省高校重点实验室四川自贡 643000
^b 中国石油大学(北京)克拉玛依校区石油学院新疆克拉玛依 834000
^c 国家管网集团工程质量监督检验有限公司成都 610095

收稿日期:2026-03-13 修回日期:2026-04-28 发布日期:2026-06-10
基金资助:
国家自然科学基金(21502131); 四川省科技厅(2023NSFSC0097); 自贡市人才计划、四川轻化工大学科研创新团队计划(SUSE652A007); 教育部产学合作协同育人资助项目

Thiocyano-oximation of Aryl Olefins Enabled by Vitamin B₁₂ Catalysis

Ziyi Zuo^a, You Lü^b^,^c, Yanping Huang^a, Xiaoqiang Liu^b^,^*(), Yu Qian^a^,^*(), Yi Yang^a^,^*()

^a Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan, Innovation Center for Chenguang High Performance Fluorine Material, Sichuan University of Science and Engineering, Zigong, Sichuan 643000
^b School of Petroleum, China University of Petroleum-Beijing at Karamay, Karamay, Xinjiang 834000
^c PipeChina Engineering Quality Supervision and Inspection Company, Chengdu 610095

Received:2026-03-13 Revised:2026-04-28 Published:2026-06-10
Contact:
^* E-mail: yangyiyoung@163.com;
125984702@qq.com;
xqliu@cupk.edu.cn
Supported by:
National Natural Science Foundation of China(21502131); Science & Technology Department of Sichuan Province(2023NSFSC0097); Zigong Talent Program, the Scientific Research and Innovation Team Program of Sichuan University of Science and Engineering(SUSE652A007); University-Industry Collaborative Education Program of the Ministry of Education

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摘要/Abstract

追求可持续性是现代有机合成的理想目标之一. 维生素B₁₂作为自然进化创造的有机钴类辅酶, 具有价廉易得、来源丰富、低毒高效等特点, 近年来广泛应用于有机合成的绿色和可持续化等领域. 报道了一种维生素B₁₂催化的芳基烯烃硫氰化/肟化双官能团化反应, 为快速向有机分子引入富含杂原子的硫氰基和肟基提供解决方案. 该反应基于维生素B₁₂的钴中心氧化还原和自由基可逆载体属性, 利用自旋离域的亲电性SCN自由基与芳基烯烃富电子双键的极性匹配效应, 使该反应表现出良好的芳基烯烃/脂肪烯烃反应选择性. 此外, 通过克级规模合成的可行性验证以及对复杂分子的后期官能化修饰应用, 进一步体现了该合成方法的实用价值.

关键词: 硫氰化-肟化, 芳基烯烃, 维生素B₁₂, 可持续催化, 自由基反应

Achieving high sustainability stands as an ideal goal in modern organic synthesis. Vitamin B₁₂, as a sustainable organocobalt coenzyme crafted by the nature, has continuously advanced the innovations of eco-friendly synthetic methodologies over recent years. Efforts toward the development of vitamin B₁₂-catalyzed thiocyano-oximation of aryl olefins are reported herein. This synthetic method highlights the tandem and regioselective stitching of medicinally-privileged dense heteroatom motifs SCN and =NOH across the aryl olefins. The high reaction-site selectivity of aryl olefins over aliphatic alkenes was achieved by capitalizing radical polarity match and the tailored reversible radical carriers of vitamin B₁₂. The usefulness of this protocol is further demonstrated by the gram-scale synthetic applicability and late-stage functionalization of several complex and value-added olefinic molecules.

Key words: thiocyano-oximation, aryl olefins, vitamin B₁₂, sustainable catalysis, radical reaction

引用此文

左子沂, 吕游, 黄艳萍, 刘晓强, 钱宇, 杨义. 维生素B₁₂催化的芳基烯烃硫氰化/肟化反应研究[J]. 有机化学, 2026, 46(10): 4098-4107.

Ziyi Zuo, You Lü, Yanping Huang, Xiaoqiang Liu, Yu Qian, Yi Yang. Thiocyano-oximation of Aryl Olefins Enabled by Vitamin B₁₂ Catalysis[J]. Chinese Journal of Organic Chemistry, 2026, 46(10): 4098-4107.

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Chemical species	Ionization energy/eV	Electron affinity/eV	ω/eV	HOMO/eV	LUMO/eV	△E_g/eV
•SCN	10.26	3.49	3.50	-8.55^a	-0.31	8.24
•SCF₃	12.59	3.17	3.29	-7.84	-5.60	2.23
Styrene	—	—	—	-6.18	-1.03	5.15
Ethene	—	—	—	-7.40	0.26	7.66
Ph•CHCH₂SCN	7.34	2.93	2.99	-7.10	-3.29	3.81
•CH₂CH₂SCN	7.62	3.21	3.32	-7.22	-3.21	3.32

Chemical species	Ionization energy/eV	Electron affinity/eV	ω/eV	HOMO/eV	LUMO/eV	△E_g/eV
•SCN	10.26	3.49	3.50	-8.55^a	-0.31	8.24
•SCF₃	12.59	3.17	3.29	-7.84	-5.60	2.23
Styrene	—	—	—	-6.18	-1.03	5.15
Ethene	—	—	—	-7.40	0.26	7.66
Ph•CHCH₂SCN	7.34	2.93	2.99	-7.10	-3.29	3.81
•CH₂CH₂SCN	7.62	3.21	3.32	-7.22	-3.21	3.32

Entry^a	Variation from the standard condition	Yield^b
1	None	2a: 84%＋3a: trace
2	NaSCN^c	2a: 64%＋3a: trace
3	KSCN^c	2a: 59%＋3a: trace
4	Me₂CHCH₂ONO^d	2a: trace＋3a: 23%
5	Me₂CHCH₂CH₂ONO^d	2a: trace＋3a: 31%
6	NaNO₂^d	N.R.
7	CoCl₂^e	2a: 52%＋3a: trace
8	CoBr₂^e	2a: 34%＋3a: trace
9	Co(BF₄)₂•6H₂O^e	2a: 33%＋3a: trace
10	Co₂O₃^e	2a: 23%＋3a: trace
11	Chloro(pyridine)cobaloxime(III)^e	2a: 44%＋3a: <5%
12	CoCl₂/Phthalocyanine^e	2a: 35%＋3a: <5%
13	CoCl₂/Tetraphenylporphyrin^e	2a: 42%＋3a: <5%
14	CH₂Cl₂^f	2a: 16%＋3a: trace
15	CH₃CN^f	2a: <10%＋3a: trace
16	EtOAc^f	2a: <10%＋3a: trace
17	Acetone^f	2a: <10%＋3a: trace
18	w/o catalyst^g	2a: <10%＋3a: trace

Entry^a	Variation from the standard condition	Yield^b
1	None	2a: 84%＋3a: trace
2	NaSCN^c	2a: 64%＋3a: trace
3	KSCN^c	2a: 59%＋3a: trace
4	Me₂CHCH₂ONO^d	2a: trace＋3a: 23%
5	Me₂CHCH₂CH₂ONO^d	2a: trace＋3a: 31%
6	NaNO₂^d	N.R.
7	CoCl₂^e	2a: 52%＋3a: trace
8	CoBr₂^e	2a: 34%＋3a: trace
9	Co(BF₄)₂•6H₂O^e	2a: 33%＋3a: trace
10	Co₂O₃^e	2a: 23%＋3a: trace
11	Chloro(pyridine)cobaloxime(III)^e	2a: 44%＋3a: <5%
12	CoCl₂/Phthalocyanine^e	2a: 35%＋3a: <5%
13	CoCl₂/Tetraphenylporphyrin^e	2a: 42%＋3a: <5%
14	CH₂Cl₂^f	2a: 16%＋3a: trace
15	CH₃CN^f	2a: <10%＋3a: trace
16	EtOAc^f	2a: <10%＋3a: trace
17	Acetone^f	2a: <10%＋3a: trace
18	w/o catalyst^g	2a: <10%＋3a: trace

维生素B₁₂催化的芳基烯烃硫氰化/肟化反应研究

Thiocyano-oximation of Aryl Olefins Enabled by Vitamin B₁₂ Catalysis

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