全碳体系的5-endo-Trig自由基环化反应研究进展

doi:10.6023/cjoc202209029

摘要/Abstract

5-endo-trig自由基环化是快速构筑五元环的理想方法之一. Baldwin-Beckwith规则指出, 受立体电子效应影响, 5-endo-trig自由基环化通常是动力学不利的. 近年来, 化学工作者一直致力于探索促进5-endo-trig自由基环化的新策略, 以期发展高效、高选择性的五元碳环或杂环化合物的合成方法. 综述了4-戊烯基自由基5-endo环化的最新进展, 总结归纳了主要的促进策略, 希望推动5-endo-trig自由基环化反应的进一步设计和发展.

关键词: 自由基, 5-endo-trig环化, 五元环, 构象限制, 极性效应

The 5-endo-trig radical closure has emerged as an ideal method for the fast aseembly of five-membered rings. It is believed to be kinetically disfavored due to the stereoelectronic disadvantages, so it is recognized as a disfavored process according to the Baldwin-Beckwith rules. Despite the challenges, continuous efforts have been devoted to develop effective strategies that enable 5-endo-trig radical cyclization. The recent advances on 5-endo-trig closure of 4-pentenyl radicals are summarized and the common strategies for accelerating the cyclization are analyzed, which will be valuable for the design and development of novel radical 5-endo-trig processes.

Key words: radical, 5-endo-trig cyclization, five-membered rings, conformational constraint, polar effect

引用此文

郑汉良, 苏静雯, 周雨露, 朱钢国. 全碳体系的5-endo-Trig自由基环化反应研究进展[J]. 有机化学, 2022, 42(12): 4060-4066.

Hanliang Zheng, Jingwen Su, Yulu Zhou, Gangguo Zhu. Recent Advances on 5-endo-Trig Radical Cyclization of All-Carbon Systems[J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4060-4066.

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图/表 10

图式1. 5-endo-trig环化的立体电子效应

Scheme 1. Stereoelectronic effects of 5-endo-trig closure

Entry	R¹	R²	R³	Yield/%
Entry	R¹	R²	R³	2	3
1	ⁱPr	Me	H	0	88
2	ⁱBu	Me	H	52	33
3	Bn	Me	Me	7	72
4	H	Me	Me	73	14
5	Et	H	H	58	21

表1. 取代基对溴代三甲基硅基炔丙基醚5-endo-trig自由基环化反应的影响

Table 1. Effect of substituents on the 5-endo-trig cyclization of bromomethyldimethylsilyl propargyl ethers.

图式2. 烯炔的[2+2+1]自由基碳环化反应

Scheme 2. [2+2+1] radical cyclization of enynes

图式3. 1,7-烯炔与环烷烃的[2+2+1]自由基环化反应

Scheme 3. [2+2+1] radical cyclization of 1,7-enynes and cycloalkanes

图式4. 1,7-烯炔与烷基腈或酮的[2+2+1]环化反应

Scheme 4. [2+2+1] radical cyclization of 1,7-enynes with alkyl nitriles or acetones

图式5. 不同自由基前体与烯炔的[2+2+1]环化反应

Scheme 5. [2+2+1] radical cyclization of enynes with various radical precursors

图式6. 稳态自由基效应促进的5-endo-trig环化反应

Scheme 6. Persistent radical effect promoted 5-endo-trig radical cyclization.

图式7. 无痕导向的炔烃磺化/5-endo碳环化反应

Scheme 7. Traceless directing 5-endo sulfonylcarbocyclization of alkynes

图式8. 炔酮的三氟甲基化/5-endo碳环化反应

Scheme 8. 5-endo-trifluoromethylcarbocyclization of ynones

图式9. 烷基醛与炔烃的自由基[3+2]环加成反应

Scheme 9. Radical [3+2] cycloaddition of alkyl aldehydes and alkynes

参考文献 28

[1]	For selected reviews, see: (a) Roche, S. P.; Aitken, D. J. Eur. J. Org. Chem. 2010, 2010, 5339. doi: 10.1002/ejoc.201000704 pmid: 27101336
	(b) Brian, H. Curr. Org. Chem. 2014, 18, 641. doi: 10.2174/13852728113176660150 pmid: 27101336
	(c) Wang, Y.; Yu, Z.-X. Acc. Chem. Res. 2015, 48, 2288. doi: 10.1021/acs.accounts.5b00037 pmid: 27101336
	(d) Simeonov, S. P.; Nunes, J. P. M.; Guerra, K.; Kurteva, V. B.; Afonso, C. A. M. Chem. Rev. 2016, 116, 5744. doi: 10.1021/cr500504w pmid: 27101336
	For recent examples, see: (e) Su, X.; Chen, B.; Wang, S.; Chen, H.; Chen, C. ACS Catal. 2018, 8, 7760. doi: 10.1021/acscatal.8b02448 pmid: 27101336
	(f) Zhao, Q.-Q.; Zhou, X.-S.; Xu, S.-H.; Wu, Y.-L.; Xiao, W.-J.; Chen, J.-R. Org. Lett. 2020, 22, 2470. doi: 10.1021/acs.orglett.0c00712 pmid: 27101336
	(g) Chai, W.; Zhou, Q.; Ai, W.; Zheng, Y.; Qin, T.; Xu, X.; Zi, W. J. Am. Chem. Soc. 2021, 143, 3595. doi: 10.1021/jacs.0c13412 pmid: 27101336
	(h) Tang, N.; Xu, Y.; Niu, T.; Yang, S.; Dong, H.; Wu, X.; Zhu, C. Org. Chem. Front. 2021, 8, 3118. doi: 10.1039/D1QO00201E pmid: 27101336
	(i) Ding, Z.; Liu, Z.; Wang, Z.; Yu, T.; Xu, M.; Wen, J.; Yang, K.; Zhang, H.; Xu, L.; Li, P. J. Am. Chem. Soc. 2022, 144, 8870. doi: 10.1021/jacs.2c03673 pmid: 27101336
	(j) Kumar, M.; Verma, S.; Mishra, V.; Reiser, O.; Verma, A. K. J. Org. Chem. 2022, 87, 6263. doi: 10.1021/acs.joc.2c00491 pmid: 27101336
	(k) Meng, F.-T.; Chen, J.-L.; Qin, X.-Y.; Zhang, T.-S.; Tu, S.-J.; Jiang, B.; Hao, W.-J. Org. Chem. Front. 2022, 9, 140. doi: 10.1039/D1QO01313K pmid: 27101336
	(l) Meng, F.-T.; Qin, X.-Y.; Li, J.; Zhang, T.-S.; Tu, S.-J.; Jiang, B.; Hao, W.-J. Chin. J. Chem. 2022, 40, 687. doi: 10.1002/cjoc.202100734 pmid: 27101336
[2]	For selected reviews, see: (a) Xu, C.-H.; Li, Y.; Li, J.-H.; Xiang, J.-N.; Deng, W. Sci. China Chem. 2019, 62, 1463. doi: 10.1007/s11426-019-9615-0
	(b) Liao, J.; Yang, X.; Ouyang, L.; Lai, Y.; Huang, J.; Luo, R. Org. Chem. Front. 2021, 8, 1345. doi: 10.1039/D0QO01453B
[3]	For selected reviews, see: (a) Dénès, F.; Beaufils, F.; Renaud, P. Synlett 2008, 2389. pmid: 28585948
	(b) Xuan, J.; Studer, A. Chem. Soc. Rev. 2017, 46, 4329. doi: 10.1039/c6cs00912c pmid: 28585948
	(d) Deepthi, A.; Sathi, V.; Nair, V. Tetrahedron Lett. 2018, 59, 2767. doi: 10.1016/j.tetlet.2018.06.029 pmid: 28585948
	(e) Yue, B.; Wu, X.; Zhu, C. Chin. J. Org. Chem. 2022, 42, 458. (in Chinese) doi: 10.6023/cjoc202108027 pmid: 28585948
	( 乐柏佟, 吴新鑫, 朱晨, 有机化学, 2022, 42, 458.) doi: 10.6023/cjoc202108027 pmid: 28585948
[4]	(a) Baldwin, J. E.; Cutting, J.; Dupont, W.; Kruse, L.; Silberman, L.; Thomas, R. C. J. Chem. Soc., Chem. Commun. 1976, 736. pmid: 12207532
	(b) Beckwith, A. L. J.; Easton, C. J.; Serelis, A. K. J. Chem. Soc., Chem. Commun. 1980, 482. pmid: 12207532
	(c) Chatgilialoglu, C.; Ferreri, C.; Guerra, M.; Timokhin, V.; Froudakis, G.; Gimisis, T. J. Am. Chem. Soc. 2002, 124, 10765. pmid: 12207532
[5]	(a) Bürgi, H. B.; Dunitz, J. D.; Lehn, J. M.; Wipff, G. Tetrahedron 1974, 30, 1563. doi: 10.1016/S0040-4020(01)90678-7
	(b) Bürgi, H. B.; Dunitz, J. D. Acc. Chem. Res. 1983, 16, 153. doi: 10.1021/ar00089a002
[6]	Ishibashi, H.; Sato, T.; Ikeda, M. Synthesis 2002, 695.
[7]	(a) Chatgilialoglu, C.; Ferreri, C.; Guerra, M.; Timokhin, V.; Froudakis, G.; Gimisis, T. J. Am. Chem. Soc. 2002, 124, 10765. pmid: 21861478
	(b) Alabugin, I. V.; Timokhin, V. I.; Abrams, J. N.; Manoharan, M.; Abrams, R.; Ghiviriga, I. J. Am. Chem. Soc. 2008, 130, 10984. doi: 10.1021/ja801478n pmid: 21861478
	(c) Alabugin, I. V.; Gilmore, K.; Manoharan, M. J. Am. Chem. Soc. 2011, 133, 12608. doi: 10.1021/ja203191f pmid: 21861478
	(d) Gilmore, K.; Alabugin, I. V. Chem. Rev. 2011, 111, 6513. doi: 10.1021/cr200164y pmid: 21861478
	(e) Gilmore, K.; Mohamed, R. K.; Alabugin, I. V. Wires Comput. Mol. Sci. 2016, 6, 487. doi: 10.1002/wcms.1261 pmid: 21861478
	(f) Huang, M.; Jia, Z.; Luo, S.; Cheng, J.-P. Chin. J. Org. Chem. 2021, 41, 3892. (in Chinese) doi: 10.6023/cjoc202106018 pmid: 21861478
	( 黄谋新, 贾宗宾, 罗三中, 程津培, 有机化学, 2021, 41, 3892.) pmid: 21861478
[8]	Bogen, S.; Gulea, M.; Fensterbank, L.; Malacria, M. J. Org. Chem. 1999, 64, 4920. doi: 10.1021/jo9904260
[9]	Bogen, S.; Goddard, J.-P.; Fensterbank, L.; Malacria, M. ARKIVOC 2008, 126.
[10]	For selected reviews, see: (a) Li, W.; Xu, W.; Xie, J.; Yu, S.; Zhu, C. Chem. Soc. Rev. 2018, 47, 654. doi: 10.1039/C7CS00507E pmid: 34123240
	(b) Stateman, L. M.; Nakafuku, K. M.; Nagib, D. A. Synthesis 2018, 50, 1569. doi: 10.1055/s-0036-1591930 pmid: 34123240
	(c) Sarkar, S.; Cheung, K. P. S.; Gevorgyan, V. Chem. Sci. 2020, 11, 12974. doi: 10.1039/d0sc04881j pmid: 34123240
	(d) Guo, W.; Wang, Q.; Zhu, J. Chem. Soc. Rev. 2021, 50, 7359. doi: 10.1039/D0CS00774A pmid: 34123240
	(e) Wu, X.; Zhu, C. Trends. Chem. 2022, 4, 580. doi: 10.1016/j.trechm.2022.04.003 pmid: 34123240
[11]	Hu, M.; Fan, J.-H.; Liu, Y.; Ouyang, X.-H.; Song, R.-J.; Li, J.-H. Angew. Chem. Int. Ed. 2015, 54, 9577. doi: 10.1002/anie.201504603
[12]	Qiu, J.-K.; Jiang, B.; Zhu, Y.-L.; Hao, W.-J.; Wang, D.-C.; Sun, J.; Wei, P.; Tu, S.-J.; Li, G. J. Am. Chem. Soc. 2015, 137, 8928. doi: 10.1021/jacs.5b05735 pmid: 26131954
[13]	Jiang, B.; Li, J.; Pan, Y.; Hao, W.; Li, G.; Tu, S. Chin. J. Chem. 2017, 35, 323. doi: 10.1002/cjoc.201600571
[14]	Hu, M.; Zou, H.-X.; Song, R.-J.; Xiang, J.-N.; Li, J.-H. Org. Lett. 2016, 18, 6460. doi: 10.1021/acs.orglett.6b03352
[15]	Gao, F.; Yang, C.; Ma, N.; Gao, G.-L.; Li, D.; Xia, W. Org. Lett. 2016, 18, 600. doi: 10.1021/acs.orglett.5b03662
[16]	Hu, M.; Song, R.-J.; Ouyang, X.-H.; Tan, F.-L.; Wei, W.-T.; Li, J.-H. Chem. Commun. 2016, 52, 3328. doi: 10.1039/C5CC10132H
[17]	Li, Y.; Liu, B.; Song, R.-J.; Wang, Q.-A.; Li, J.-H. Adv. Synth. Catal. 2016, 358, 1219. doi: 10.1002/adsc.201501134
[18]	Qu, Y.; Xu, W.; Zhang, J.; Liu, Y.; Li, Y.; Song, H.; Wang, Q. J. Org. Chem. 2020, 85, 5379. doi: 10.1021/acs.joc.0c00087
[19]	Li, J.; Hao, W.-J.; Zhou, P.; Zhu, Y.-L.; Wang, S.-L.; Tu, S.-J.; Jiang, B. RSC Adv. 2017, 7, 9693. doi: 10.1039/C6RA28589A
[20]	Jiao, M.-J.; Liu, D.; Hu, X.-Q.; Xu, P.-F. Org. Chem. Front. 2019, 6, 3834. doi: 10.1039/C9QO01166H
[21]	Correia, J. T. M.; Piva da Silva, G.; André, E.; Paixão, M. W. Adv. Synth. Catal. 2019, 361, 5558. doi: 10.1002/adsc.201900657
[22]	Liu, H.-Y.; Lu, Y.; Li, Y.; Li, J.-H. Org. Lett. 2020, 22, 8819. doi: 10.1021/acs.orglett.0c03182
[23]	Yu, J.-X.; Teng, F.; Xiang, J.-N.; Deng, W.; Li, J.-H. Org. Lett. 2019, 21, 9434. doi: 10.1021/acs.orglett.9b03643
[24]	Šimek, M.; Bártová, K.; Pohl, R.; Císařová, I.; Jahn, U. Angew. Chem. Int. Ed. 2020, 59, 6160. doi: 10.1002/anie.201916188
[25]	Zhou, Y.; Qin, Y.; Wang, Q.; Zhang, Z.; Zhu, G. Angew. Chem. Int. Ed. 2022, 61, e202110864.
[26]	For selected reviews, see: (a) Roberts, B. P. Chem. Soc. Rev. 1999, 28, 25. doi: 10.1039/a804291h
	(b) Parsaee, F.; Senarathna, M. C.; Kannangara, P. B.; Alexander, S. N.; Arche, P. D. E.; Welin, E. R. Nat. Rev. Chem. 2021, 5, 486. doi: 10.1038/s41570-021-00284-3
[27]	(a) Le, S.; Bai, Y.; Qiu, J.; Zhang, Z.; Zheng, H.; Zhu, G. Org. Chem. Front. 2022, 9, 4670. doi: 10.1039/D2QO00843B
	(b) Qiu, J.; Le, S.; Su, J.; Liu, Y.; Zhou, Y.; Zheng, H.; Bai, Y.; Zhu, G. Org. Chem. Front. 2022, 9, 5523. doi: 10.1039/D2QO01101H
[28]	Le, S.; Li, J.; Feng, J.; Zhang, Z.; Bai, Y.; Yuan, Z.; Zhu, G. Nat. Commun. 2022, 13, 4734. doi: 10.1038/s41467-022-32467-x