亚硝基苯参与的电化学串联环化反应构建喹啉/吡咯

doi:10.6023/cjoc202307002

摘要/Abstract

报道了一种多取代喹啉/吡咯杂环化合物的电化学合成新方法. 反应以亚硝基苯和贫电子内炔为起始物, 在无需额外金属催化剂、室温条件下, 通过阴极单电子还原的策略, 选择性地还原亚硝基苯产生亚硝基自由基, 随后与炔烃进行串联环化反应, 绿色、高效地合成了一系列具有高附加值的多取代喹啉/吡咯杂环化合物.

关键词: 电化学合成, 串联环化, 亚硝基苯

A novel electrochemical cascade cyclization between nitrosobenzene and electron-deficient alkynes was developed in this work. The use of electroreduction for the activation of nitrosobenzene which highlighted the unique possibilities associated with electrochemical activation methods. This protocol represents a simple, efficient, and environmentally benign way to construct substituted quinolines and pyrroles in good yields with high selectivity.

Key words: electrosynthesis, cascade cyclization, nitrosobenzene

引用此文

杨帆, 方婷, 杨桂春, 高梦. 亚硝基苯参与的电化学串联环化反应构建喹啉/吡咯[J]. 有机化学, 2024, 44(3): 1021-1030.

Fan Yang, Ting Fang, Guichun Yang, Meng Gao. Electrochemical Cascade Cyclization Reactions of Nitrosobenzenes in Construction of Quinolines and Pyrroles[J]. Chinese Journal of Organic Chemistry, 2024, 44(3): 1021-1030.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 8

图式1. 亚硝基苯参与的电化学串联环化反应

Scheme 1. Electrochemical cascade cyclization of nitrosobenzenes

Entry	Variation from the standard condition^a	Yield^b/%
1	None	74
2	C/Ni	38
3	C/Zn	51
4	ⁿBu₄NClO₄ instead of ⁿBu₄NI	Trace
5	ⁿBu₄NBr instead of ⁿBu₄NI	15
6	KI instead of ⁿBu₄NI	36
7	MeCN	46
8	10 mA	48
9	5 mA	37
10	No electricity	n.d.

表1. 多取代喹啉3aa的反应条件优化a

Table 1. Reaction optimization of polysubstituted quinoline 3aa

表2. 多取代喹啉的合成a

Table 2. Synthesis of polysubstituted quinolines

Entry	Variation from the standard condition^a	Yield^b/%
1	None	63
2	Without DIPEA	32
3	No electricity	n.d.

表3. 多取代吡咯4aa的反应条件优化a

Table 3. Reaction optimization of polysubstituted pyrroles 4aa

表4. 多取代吡咯杂环的合成a

Table 4. Synthesis of polysubstituted pyrroles

图式2. 机理实验

Scheme 2. Mechanistic experiments

图1. ESI-MS从反应溶液中检测到的A和B的关键片段归属

Figure 1. Key fragments assignment of A and B detected from the reaction solution by ESI-MS

图2. 构建吡咯环的吉布斯自由能计算图谱

Figure 2. Calculated Gibbs free energy profile for the construction of pyrrole ring

参考文献 15

[1]	(a) Pozharskii A. F.; Katritzky A. R.; Soldatenkov A. T. Heterocycles in Life and Society: an Introduction to Heterocyclic Chemistry, Biochemisttry, and Applications, 2nd ed., Wiley, Chichester, 2011.
	(b) Katritzky A. R. Comprehensive Heterocyclic Chemistry III, 1st ed.ed., Elsevier, Amsterdam, 2008.
[2]	(a) Huang S; Huo H.; Li W.; Hong R. Chin. J. Org. Chem. 2012, 32, 1776. (in Chinese) doi: 10.6023/cjoc201207026
	( 黄莎华, 霍华兴, 李文华, 洪然, 有机化学, 2012, 32, 1776.) doi: 10.6023/cjoc201207026
	(b) Adam W.; Krebs O. Chem. Rev. 2003, 103, 4131. doi: 10.1021/cr030004x
	(c) Gao Y.; Yang S.; Xiao W.; Nie J.; Hu X.-Q. Chem. Commun. 2020, 56, 13719. doi: 10.1039/D0CC06023B
	(d) Huang J.; Chen Z.; Yuan J.; Peng Y. Asian J. Org. Chem. 2016, 5, 951. doi: 10.1002/ajoc.v5.8
	(e) Yamamoto H.; Momiyama N. Chem. Commun. 2005, 3514.
[3]	(a) Murru S.; Gallo A. A.; Srivastava R. S. ACS Catal. 2011, 1, 29. doi: 10.1021/cs100024n
	(b) Murru S.; Gallo A. A.; Srivastava R. S. Eur. J. Org. Chem. 2011, 2011, 2035.
	(c) Penoni A.; Volkmann J.; Nicholas K. M. Org. Lett. 2002, 4, 699. doi: 10.1021/ol017139e
	(d) Penoni A.; Palmisano G.; Zhao Y.-L.; Houk K. N.; Volkman J.; Nicholas K. M. J. Am. Chem. Soc. 2009, 131, 653. doi: 10.1021/ja806715u
[4]	(a) Bodnar B. S.; Miller M. J. Angew. Chem., Int. Ed. 2011, 50, 5630. doi: 10.1002/anie.v50.25 pmid: 25119424
	(b) Momiyama N.; Yamamoto Y.; Yamamoto H. J. Am. Chem. Soc. 2007, 129, 1190. pmid: 25119424
	(c) Maji B.; Yamamoto H. J. Am. Chem. Soc. 2015, 137, 15957. doi: 10.1021/jacs.5b11273 pmid: 25119424
	(d) Carosso S.; Miller M. J. Org. Biomol. Chem. 2014, 12, 7445. doi: 10.1039/c4ob01033g pmid: 25119424
[5]	(a) Yang Y.; Ren H.-X.; Chen F.; Zhang Z.-B.; Zou Y.; Chen C.; Song X.-J.; Tian F.; Peng L.; Wang L.-X. Org. Lett. 2017, 19, 2805. doi: 10.1021/acs.orglett.7b00893 pmid: 28485602
	(b) Hu W.; Yu J.-T.; Liu S.; Jiang Y.; Cheng J. Org. Chem. Front. 2017, 4, 22. doi: 10.1039/C6QO00540C pmid: 28485602
	(c) Purkait A.; Saha S.; Ghosh S.; Jana C. K. Chem. Commun. 2020, 56, 15032. doi: 10.1039/D0CC02650F pmid: 28485602
	(d) Purkait A.; Roy S. K.; Srivastava H. K.; Jana C. K. Org. Lett. 2017, 19, 2540. doi: 10.1021/acs.orglett.7b00832 pmid: 28485602
	(e) Chakrabarty S.; Chatterjee I.; Wibbeling B.; Daniliuc C. G.; Studer A. Angew. Chem., Int. Ed. 2014, 53, 5964. doi: 10.1002/anie.v53.23 pmid: 28485602
	(f) Wu Y.; Liu Q.; Huang S.; Zhang C.; Wei W.; Li X. Org. Biomol. Chem. 2023, 21, 3669. doi: 10.1039/D3OB00189J pmid: 28485602
	(g) Wang H.-X.; Zhang M.-M.; Xie M.-S.; Guo H.-M. Eur. J. Org. Chem. 2022, 2022, e202200604. pmid: 28485602
	(h) Li X.; Feng T.; Li D.; Chang H.; Gao W.; Wei W. J. Org. Chem. 2019, 84, 4402. doi: 10.1021/acs.joc.9b00299 pmid: 28485602
	(i) Huple D. B.; Ghorpade S.; Liu R.-S. Adv. Synth. Catal. 2016, 358, 1348. doi: 10.1002/adsc.v358.9 pmid: 28485602
	(j) Reddy A. R.; Zhou C.-Y.; Che C.-M. Org. Lett. 2014, 16, 1048. doi: 10.1021/ol4035098 pmid: 28485602
	(k) Wu M.-Y.; He W.-W.; Liu X.-Y.; Tan B. Angew. Chem., Int. Ed. 2015, 54, 9409. doi: 10.1002/anie.v54.32 pmid: 28485602
[6]	Qiu S.; Liang R.; Wang Y.; Zhu S. Org. Lett. 2019, 21, 2126. doi: 10.1021/acs.orglett.9b00426
[7]	Leach A. G.; Houk K. N. J. Am. Chem. Soc. 2002, 124, 14820. doi: 10.1021/ja012757b
[8]	(a) Ghosh S.; Kumar G.; Naveen; Pradhan S.; Chatterjee I. Chem. Commun. 2019, 55, 13590. doi: 10.1039/C9CC07277B
	(b) Kawade R. K.; Liu R.-S. Angew. Chem., Int. Ed. 2017, 56, 2035. doi: 10.1002/anie.v56.8
	(c) Kang J. Y.; Bugarin A.; Connell B. T. Chem. Commun. 2008, 3522.
	(d) Liu J.; Skaria M.; Sharma P.; Chiang Y.-W.; Liu R.-S. Chem. Sci. 2017, 8, 5482. doi: 10.1039/C7SC01770G
[9]	For selected reviews, see: a Jiang, Y.; Xu, K.; Zeng, C. Chem. Rev. 2018, 118, 4485. doi: 10.1021/acs.chemrev.7b00271
	(b) Kärkäs M. D. Chem. Soc. Rev. 2018, 47, 5786. doi: 10.1039/C7CS00619E
	(c) Ma C.; Fang P.; Mei T.-S. ACS Catal. 2018, 8, 7179. doi: 10.1021/acscatal.8b01697
	(d) Tang S.; Liu Y.; Lei A. Chem 2018, 4, 27. doi: 10.1016/j.chempr.2017.10.001
	(e) Xiong P.; Xu H.-C. Acc. Chem. Res. 2019, 52, 3339. doi: 10.1021/acs.accounts.9b00472
	(f) Yan M.; Kawamata Y.; Baran P. S. Chem. Rev. 2017, 117, 13230. doi: 10.1021/acs.chemrev.7b00397
	For selected research works see:
	(g) Chen D.; Yang X.; Wang D.; Li Y.; Shi L.; Liang D. Org. Chem. Front. 2023, 10, 2482 doi: 10.1039/D3QO00290J
	(h) Ma Z.; Hu X.; Li Y.; Liang D.; Dong Y.; Wang B.; Li W. Org. Chem. Front. 2021, 8, 2208. doi: 10.1039/D1QO00168J
[10]	Yuan Y.; Lei A. Nat. Commun. 2020, 11, 802. doi: 10.1038/s41467-020-14322-z
[11]	Wang D.; Tamizmani M.; Leng X.; Deng L. Chin. J. Chem. 2020, 38, 158. doi: 10.1002/cjoc.v38.2
[12]	(a) Gronchi G.; Courbis P.; Tordo P.; Mousset G.; Simonet J. J. Phys. Chem. 1983, 87, 1343. doi: 10.1021/j100231a015
	(b) Mugnier Y.; Gard J.; Huang Y.; Couture Y.; Lasia A.; Lessard J. J. Org. Chem. 1993, 58, 5329. doi: 10.1021/jo00072a011
[13]	Priewisch B.; Rück-Braun K. J. Org. Chem. 2005, 70, 2350. pmid: 15760229
[14]	Wang Y.; Hoye T. R. Org. Lett. 2018, 20, 4425. doi: 10.1021/acs.orglett.8b01705
[15]	Mal K.; Chatterjee S.; Bhaumik A.; Mukhopadhyay C. ChemistrySelect 2019, 4, 1776. doi: 10.1002/slct.v4.5