Thiocyano-oximation of Aryl Olefins Enabled by Vitamin B12 Catalysis

doi:10.6023/cjoc202603016

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (10): 4098-4107.DOI: 10.6023/cjoc202603016 Previous Articles Next Articles

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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
通讯作者: 刘晓强, 钱宇, 杨义
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: Xiaoqiang Liu, Yu Qian, Yi Yang
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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Abstract

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

Cite this article

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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References 39

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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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维生素B12催化的芳基烯烃硫氰化/肟化反应研究