Cobalt-Catalyzed Regio- and Stereoselective Isomerization of Terminal Alkenes to trans-2-Alkenes

doi:10.6023/cjoc202404018

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (9): 2889-2897.DOI: 10.6023/cjoc202404018 Previous Articles Next Articles

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钴催化末端烯烃区域和立体选择性异构合成反式-2-烯烃

杜佳言^a^,^b, 刘俊涛^b^,^c, 刘桂霞^b^,^*(), 黄正^b^,^c^,^*()

a 上海科技大学物质科学与技术学院上海 201210
b 中国科学院上海有机化学研究所金属有机化学国家重点实验室中国科学院大学上海 200032
c 国科大杭州高等研究院化学与材料科学学院杭州 310024

收稿日期:2024-04-12 修回日期:2024-05-06 发布日期:2024-05-10
通讯作者: 刘桂霞, 黄正
作者简介:
^†共同第一作者.
基金资助:
国家重点研发计划(2021YFA1500100); 国家自然科学基金(21825109); 国家自然科学基金(21821002); 国家自然科学基金(22072178); 国家自然科学基金(22293013); 中国科学院战略性先导科技专项(XDB0610000); 中国科学院稳定支持基础研究领域青年团队计划(YSBR-094); 上海市科学技术委员会(23JC1404400); 中科院青年交叉团队(JCTD-2021-11)

Cobalt-Catalyzed Regio- and Stereoselective Isomerization of Terminal Alkenes to trans-2-Alkenes

Jiayan Du^a^,^b, Juntao Liu^b^,^c, Guixia Liu^b(), Zheng Huang^b^,^c()

a School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032
c School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024

Received:2024-04-12 Revised:2024-05-06 Published:2024-05-10
Contact: Guixia Liu, Zheng Huang
About author:
^†These authors contributed equally to this work.
Supported by:
National Key R&D Program of China(2021YFA1500100); National Natural Science Foundation of China(21825109); National Natural Science Foundation of China(21821002); National Natural Science Foundation of China(22072178); National Natural Science Foundation of China(22293013); Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000); CAS Project for Young Scientists in Basic Research(YSBR-094); Science and Technology Commission of Shanghai Municipality(23JC1404400); CAS Youth Interdisciplinary Team(JCTD-2021-11)

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Abstract

An efficient and E-selective monoisomerization of 1-alkenes is developed with a bis(phosphine)-based PCP-type Co complex as the catalyst. The protocol provides an atom-economical approach to trans-2-alkenes with high regio- and stereoselectivity, featuring mild conditions and wide substrate scope. Mechanistic investigation supports a cobalt-hydride pathway involving reversible alkene insertion/β-H elimination, and the step of β-H elimination at the allylic position is likely the rate-determining step.

Key words: cobalt catalysis, alkenes, isomerization, regioselectivity, stereoselectivity

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Jiayan Du, Juntao Liu, Guixia Liu, Zheng Huang. Cobalt-Catalyzed Regio- and Stereoselective Isomerization of Terminal Alkenes to trans-2-Alkenes[J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2889-2897.

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Entry	[Co]	Solvent	Time/h	Conv./%	Yield/% of 2a (E∶Z)	Yield/% of 3- or 4-octene
1	3a	THF	1	42	41 (9∶1)	1
2	3a	Hexane	1	97	92 (4∶1)	5
3	3a	Toluene	1	97	88 (6∶1)	9
4	3a	CH₃CN	1	0
5	3a	Diethyl ether	1	67	65 (11∶1)	2
6	3a	Diethyl ether	2	78	76 (11∶1)	2
7	3a	Diethyl ether	2.75	98	93 (11∶1)	5
8	3a	Diethyl ether	3	98	80 (8∶1)	18
9	3a	Diethyl ether	24	99	69 (6∶1)	30
10	3b	Diethyl ether	2.75	45	45 (10∶1)	0
11	3c	Diethyl ether	2.75	0

Entry	[Co]	Solvent	Time/h	Conv./%	Yield/% of 2a (E∶Z)	Yield/% of 3- or 4-octene
1	3a	THF	1	42	41 (9∶1)	1
2	3a	Hexane	1	97	92 (4∶1)	5
3	3a	Toluene	1	97	88 (6∶1)	9
4	3a	CH₃CN	1	0
5	3a	Diethyl ether	1	67	65 (11∶1)	2
6	3a	Diethyl ether	2	78	76 (11∶1)	2
7	3a	Diethyl ether	2.75	98	93 (11∶1)	5
8	3a	Diethyl ether	3	98	80 (8∶1)	18
9	3a	Diethyl ether	24	99	69 (6∶1)	30
10	3b	Diethyl ether	2.75	45	45 (10∶1)	0
11	3c	Diethyl ether	2.75	0

钴催化末端烯烃区域和立体选择性异构合成反式-2-烯烃

Cobalt-Catalyzed Regio- and Stereoselective Isomerization of Terminal Alkenes to trans-2-Alkenes

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