Hydrocarboxylation of Alkenes with Formate Salts via Photocatalysis

doi:10.6023/cjoc202202008

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (8): 2568-2573.DOI: 10.6023/cjoc202202008 Previous Articles Next Articles

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可见光诱导甲酸盐参与的烯烃氢羧化反应

黄燕, 张谦, 詹乐武, 侯静^*(), 李斌栋^*()

南京理工大学化学与化工学院南京 210094

收稿日期:2022-02-08 修回日期:2022-04-11 发布日期:2022-04-22
通讯作者: 侯静, 李斌栋
作者简介:
^† 共同第一作者
基金资助:
国家自然科学基金(21901118); 江苏省自然科学基金(BK20190430); 重点高校基础科研业务费专项资金(30921011206)

Hydrocarboxylation of Alkenes with Formate Salts via Photocatalysis

Yan Huang, Qian Zhang, Lewu Zhan, Jing Hou(), Bindong Li()

College of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094

Received:2022-02-08 Revised:2022-04-11 Published:2022-04-22
Contact: Jing Hou, Bindong Li
About author:
^† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21901118); Natural Science Foundation of Jiangsu Province(BK20190430); Fundamental Research Funds for the Central Universities(30921011206)

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Abstract

A transition-metal-free β-selective hydrocarboxylation of alkenes under mild conditions has been developed using a formate salt as the reductant, carbonyl source. A broad range of alkenes were compatible with this method and can be efficiently converted into value-added carboxylic acid products. This method also features low catalyst loading, good functional group tolerance, and easy scalability.

Key words: alkenes, hydrocarboxylation, photocatalysis, carbon dioxide radical anion, formate salt

Cite this article

Yan Huang, Qian Zhang, Lewu Zhan, Jing Hou, Bindong Li. Hydrocarboxylation of Alkenes with Formate Salts via Photocatalysis[J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2568-2573.

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Fig. & Tab. 5

Scheme 1. Hydrocarboxylation of alkenes with formate salts via photocatalysis

Entry	Deviation	Yield^b/%
1	None	81
2	Eosin B instead of Rose Bengal	63
3	Fluorescein instead of Rose Bengal	36
4	T2 instead of T1	18
5	T3 instead of T1	47
6	1 equiv. T1	54
7	25 mol% T1	37
8	1 mol% Rose Bengal	76
9	HCOONH₄ instead of HCOOCs	55
10	HCOONa instead of HCOOCs	56
11	HCOOK instead of HCOOCs	78
12	DMF instead of DMSO	N.D.
13	NMP instead of DMSO	N.D.
14	EA instead of DMSO	32
15	Without Rose Bengal	N.D.
16	Without T1	N.D.
17	In the dark	N.D.

Table 1. Optimization of hydrocarboxylation of styrenea

Scheme 2. Scope of hydrocarboxylation of alkenes Reaction condition: 1a (0.1 mmol), HCOOCs (1.0 mmol), Rose Bengal (2 mol%), T1 (50 mol%), DMSO (3 mL), 50 ℃, 40 W blue LED (440 nm), Ar, 12 h. a 100 ℃. b Isolated yield.

Scheme 3. Control experiments: (a) radical-trapping experiment with TEMPO, (b) radical clock experiment, (c) DCOOCs deuterium labeling experiments and (d) D2O deuterium labeling experiments

Scheme 4. Proposed mechanism of hydrocarboxylation of alkenes with formate salts via photocatalysis

References 14

[1]	Kiss, G. Chem. Rev. 2001, 101, 3435. pmid: 11840990
[2]	Wu, X.-F.; Fang, X.-J.; Wu, L.-P.; Jackstell, R.; Neumann, H.; Beller, M. Acc. Chem. Res. 2014, 47, 1041. doi: 10.1021/ar400222k
[3]	Hou, Y.; Niu, M.; Wu, W. Ind. Eng. Chem. Res. 2020, 59, 16899. doi: 10.1021/acs.iecr.0c01088
[4]	Ra, E.-C.; Kim, K.-Y.; Kim, E.-H.; Lee, H.; An, K.; Lee. J.-S. ACS Catal. 2020, 10, 11318. doi: 10.1021/acscatal.0c02930
[5]	Tortajada, A.; Juliá-Hernández, F.; Börjesson, M.; Moragas, T.; Martin, R. Angew. Chem. Int. Ed. 2018, 57, 15948. doi: 10.1002/anie.201803186 pmid: 29722461
[6]	Wu, L.-P.; Liu, Q.; Jackstell, R.; Beller, M. Angew. Chem. Int. Ed. 2014, 53, 6310. doi: 10.1002/anie.201400793
[7]	Hendy, C.-M.; Smith, G.-C.; Xu, Z.-H.; Lian, T.-Q.; Jui, N.-T. J. Am. Chem. Soc. 2021, 143, 8987. doi: 10.1021/jacs.1c04427
[8]	Chmiel, A.-F.; Williams, O.-P.; Chernowsky, C.-P.; Yeung, C.-S.; Wickens. Z.-K. J. Am. Chem. Soc. 2021, 143, 10882. doi: 10.1021/jacs.1c05988 pmid: 34255971
[9]	Alektiar, S.-N.; Wickens. Z.-K. J. Am. Chem. Soc. 2021, 143, 13022. doi: 10.1021/jacs.1c07562 pmid: 34380308
[10]	Koppenol, W.-H.; Rush, J.-D. J. Phys. Chem. 1987, 91, 4429. doi: 10.1021/j100300a045
[11]	Huang, Y.; Hou, J.; Zhan, L.-W.; Zhang, Q.; Tang, W.-Y.; li, B.-D. ACS Catal. 2021, 11, 15004. doi: 10.1021/acscatal.1c04684
[12]	Péault, L.; Planchat, A.; Nun, P.; Grognec, E.-L; Coeffard. V. J. Org. Chem. 2021, 86, 18192. doi: 10.1021/acs.joc.1c02459 pmid: 34851652
[13]	Liu, W.; Ren, W.-L.; Li, J.-F.; Shi, Y.; Chang, W.-J.; Shi, Y. Org. Lett. 2017, 19, 1748. doi: 10.1021/acs.orglett.7b00507
[14]	Guđmundsson, A.; Gustafson, K.-P.-J.; Mai, B.-K.; Yang, B.; Himo, F.; Bäckvall, J.-E. ACS Catal. 2018, 8, 11134. doi: 10.1021/acscatal.8b03592

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可见光诱导甲酸盐参与的烯烃氢羧化反应

Hydrocarboxylation of Alkenes with Formate Salts via Photocatalysis

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