银催化环状醛亚胺与草酸单烷基酯的脱羧C—H烷基化反应研究

doi:10.6023/cjoc202510026

摘要/Abstract

通过C—O键断裂策略实现了银催化的单烷基草酸酯与环状醛亚胺的脱羧C(sp²)—H键烷基化反应. 该反应在温和条件下进行, 以中等至良好的收率(30%~80%)得到目标产物, 且底物适用范围广泛. 此外, 还对酪氨酸和雌酮衍生的环状醛亚胺进行了后期修饰研究, 并将该催化体系拓展应用于五元环和七元环的醛亚胺, 反应均能顺利进行, 以中等收率得到了相应产物. 机理研究表明该反应经历自由基机理.

关键词: 银催化, C—H烷基化, 环状醛亚胺, 草酸单烷基酯, C—O键断裂

Silver-catalyzed decarboxylative C(sp²)—H alkylation of cyclic aldimines with monoalkyl oxalates via C—O bond cleavage has been realized under mild reaction conditions. The corresponding products were generated in moderate to good yields (30%~80%) with wide substrate scope. In addition, the late-stage modification of tyrosine- and estrone-derived cyclic aldimines was investigated, and this catalytic system was further extended to five- and seven-membered cyclic aldimines. The reactions proceeded smoothly, affording the corresponding products in moderate yields. The mechanistic studies show that the reaction undergoes a radical pathway.

Key words: silver catalysis, C—H alkylation, cyclic aldimine, monoalkyl oxalate, C—O bond cleavage

引用此文

王晶晶, 于子涵, 岳开华, 伊茂聪, 张安东, 丁同惠, 王翠洁, 崔明月, 廖科超, 李峰. 银催化环状醛亚胺与草酸单烷基酯的脱羧C—H烷基化反应研究[J]. 有机化学, 2026, 46(5): 2096-2103.

Jingjing Wang, Zihan Yu, Kaihua Yue, Maocong Yi, Andong Zhang, Tonghui Ding, Cuijie Wang, Mingyue Cui, Kechao Liao, Feng Li. Silver-Catalyzed Decarboxylative C—H Alkylation of Cyclic Aldimines with Monoalkyl Oxalates[J]. Chinese Journal of Organic Chemistry, 2026, 46(5): 2096-2103.

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参考文献 18

[1]	(a) Majumdar K. C.; Mondal S. Chem. Rev. 2011, 111, 7749. doi: 10.1021/cr1003776 pmid: 23136854
	(b) Williams S. J. Expert Opin. Ther. Pat. 2013, 23, 79. doi: 10.1517/13543776.2013.736965 pmid: 23136854
	(c) Debnath S.; Mondal S. Eur. J. Org. Chem. 2018, 2018, 933. doi: 10.1002/ejoc.v2018.8 pmid: 23136854
[2]	(a) Peters R. H.; Chao W.-R.; Sato B.; Shigeno K.; Zaveri N. T. Tanabe M. Steroids 2003, 68, 97. doi: 10.1016/S0039-128X(02)00118-6
	(b) Woo L. L.; Purohit A.; Potter B. V. Mol. Cell. Endocrinol. 2011, 340, 175. doi: 10.1016/j.mce.2010.12.035
[3]	Ji H.-T.; Lu Y.-H.; Liu Y.-T.; Huang Y.-L.; Tian J.-F.; Liu F.; Zeng Y.-Y.; Yang H.-Y.; Zhang Y.-H.; He W.-M. Chin. Chem. Lett. 2025, 36, 110568. doi: 10.1016/j.cclet.2024.110568
[4]	Alig B.; Muller K.-H.; Franken E.-M.; Gorgens U.; Voerste A. US 8173641 B2, 2012.
[5]	For selected exam.p.les of transformations of cyclic aldimines, see: pmid: 33074678
	(a) Guin S.; Majee D.; Samanta S. Chem. Commun. 2021, 57, 9010. doi: 10.1039/D1CC03439A pmid: 33074678
	(b) Luo Y.; Carnell A. J.; Lam H. W. Angew. Chem., Int. Ed. 2012, 51, 6762. doi: 10.1002/anie.v51.27 pmid: 33074678
	(c) Zhang H.-X.; Nie J.; Cai H.; Ma J.-A. Org. Lett. 2014, 16, 2542. doi: 10.1021/ol500929d pmid: 33074678
	(d) Parthasarathy K.; Azcargorta A. R.; Cheng Y.; Bolm C. Org. Lett. 2014, 16, 2538. doi: 10.1021/ol500918t pmid: 33074678
	(e) Lai B.-N.; Qiu J.-F.; Zhang H.-X.; Nie J.; Ma J.-A. Org. Lett. 2016, 18, 520. doi: 10.1021/acs.orglett.5b03551 pmid: 33074678
	(f) Xia A.-J.; Kang T.-R.; He L.; Chen L.-M.; Li W.-T.; Yang J.-L.; Liu Q.-Z. Angew. Chem., Int. Ed. 2016, 55, 1441. doi: 10.1002/anie.v55.4 pmid: 33074678
	(g) Jia C.-M.; Zhang H.-X.; Nie J.; Ma J.-A. J. Org. Chem. 2016, 81, 8561. doi: 10.1021/acs.joc.6b01750 pmid: 33074678
	(h) Cui X.-Y.; Duan H.-X.; Zhang Y.; Wang Y.-Q. Chem.-Asian J. 2016, 11, 3118. doi: 10.1002/asia.v11.21 pmid: 33074678
	(i) Quan M.; Tang L.; Shen J.; Yang G.; Zhang W. Chem. Commun. 2017, 53, 609. doi: 10.1039/C6CC08759K pmid: 33074678
	(j) Munck L. D.; Monleón A.; Vila C.; Pedro J. R. Adv. Synth. Catal. 2017, 359, 1582. doi: 10.1002/adsc.v359.9 pmid: 33074678
	(k) Spielmann K.; Lee A.; Figueiredo R. M.; Campagne J.-M. Org. Lett. 2018, 20, 1444. doi: 10.1021/acs.orglett.8b00228 pmid: 33074678
	(l) Shi W.; Zhou L.; Mao B.; Wang Q.; Wang C.; Zhang C.; Li X.; Xiao Y.; Guo H. J. Org. Chem. 2019, 84, 679. doi: 10.1021/acs.joc.8b02515 pmid: 33074678
	(m) Zhou J.; Zhang H.; Chen X.-L.; Qu Y.-L.; Zhu Q.; Feng C.-G.; Jethava P.; Fine J.; Chen Y.; Hossain A.; Chopra G. Org. Lett. 2020, 22, 8480. doi: 10.1021/acs.orglett.0c03083 pmid: 33074678
	(n) Li Y.-L.; Liu J.-X.; Chen X.-P.; Zhou Y.; Xiao Y.-C.; Chen F.-E. Adv. Synth. Catal. 2020, 362, 3202. doi: 10.1002/adsc.v362.15 pmid: 33074678
	(o) Reddy M. K.; Bhajammanavar V.; Baidya M. Org. Lett. 2021, 23, 3868. doi: 10.1021/acs.orglett.1c01001 pmid: 33074678
	(p) Mondal S.; Aher R. D.; Bethi V.; Lin Y.-J.; Taniguchi T.; Monde K.; Tanaka F. Org. Lett. 2022, 24, 1853. doi: 10.1021/acs.orglett.2c00436 pmid: 33074678
	(q) Wang F.; Huang D.; Zhao P.; Yang M.; Han T.; Wang K.; Wang J.; Su Y.; Hu Y. Chin. J. Org. Chem. 2022, 42, 507 (in Chinese). doi: 10.6023/cjoc202108016 pmid: 33074678
	(王凤, 黄丹凤, 赵鹏飞, 杨明, 韩侗育, 王克虎, 王君姣, 苏瀛鹏, 胡雨来, 有机化学, 2022, 42, 507.) doi: 10.6023/cjoc202108016 pmid: 33074678
	(r) Rit R. K.; Li H.; Argent S. P.; Wheelhouse K. M.; Woodward S.; Lam H. W. Adv. Synth. Catal. 2023, 365, 1629. doi: 10.1002/adsc.v365.10 pmid: 33074678
	(s) Garg Y.; Osborne J.; Vasylevskyi S.; Velmurugan N.; Tanaka F. J. Org. Chem. 2023, 88, 11096. doi: 10.1021/acs.joc.3c01051 pmid: 33074678
	(t) Kim Y.; Kim Y.; Kim S.-G. Chem.-Asian J. 2024, 19, e202301011. doi: 10.1002/asia.v19.3 pmid: 33074678
	(u) Li Y.; Shi H. Chin. Chem. Lett. 2024, 35, 108650. doi: 10.1016/j.cclet.2023.108650 pmid: 33074678
	(v) Zhu Y.; Wang H.; Liu R.; Liu K.; Hu X.; Huang J.; Wang C.; Wang L.; Liu Y.; Liu G.; Tan C. Chem. Sci. 2025, 16, 4374. doi: 10.1039/D4SC07212J pmid: 33074678
	(w) Tang Y.; Xu Y.; Zhang X.; Wang C.; Zhao D.; Li F.; Wang L. ACS Catal. 2025, 15, 4784. doi: 10.1021/acscatal.4c06927 pmid: 33074678
	(x) Yi Z.; Xiao W.; Jie J.; Yang H.; Fu H. Org. Lett. 2025, 27, 6330. doi: 10.1021/acs.orglett.5c01505 pmid: 33074678
	(y) Tang Y.; Huang M.; Jin J.; Sun S.; Wang L.; Tan Y.; Sun X.; Guo H. Angew. Chem., Int. Ed. 2025, 64, e202415787. doi: 10.1002/anie.v64.4 pmid: 33074678
[6]	(a) Wang J.; Liu X.; Wu Z.; Li F.; Zhang M.-L.; Mi Y.; Wei J.; Zhou Y.; Liu L. Chem. Commun. 2021, 57, 1506. doi: 10.1039/D0CC07181A
	(b) Wang J.; Liu X.; Wu Z.; Li F.; Qin T.; Zhang S.; Kong W.; Liu L. Chin. Chem. Lett. 2021, 32, 2777. doi: 10.1016/j.cclet.2021.03.011
[7]	(a) Liu X.; Wang J.; Wu Z.; Li F.; Gao K.; Peng F.; Wang J.; Shen R.; Zhou Y.; Liu L. Org. Biomol. Chem. 2021, 19, 3595. doi: 10.1039/D1OB00223F
	(b) Shi A.; Sun K.; Chen X.; Qu L.; Zhao Y.; Yu B. Org. Lett. 2022, 24, 299. doi: 10.1021/acs.orglett.1c03960
	(c) Wang X.; Shi A.; Huang X.-Q.; Chen X.; Li T.; Qu L.; Yu B. Org. Biomol. Chem. 2022, 20, 3798. doi: 10.1039/D2OB00460G
	(d) Shi A.; Sun K.; Wu Y.; Xiang P.; Krylov I. B.; Terent’ev A. O.; Chen X.; Yu B. J. Catal. 2022, 415, 28. doi: 10.1016/j.jcat.2022.09.027
	(e) Wang H.-X.; Li Z.-H.; Li W.-W.; Qu G.-R.; Yang Q.-L.; Guo H.-M. Green Chem. 2022, 24, 8377. doi: 10.1039/D2GC03218J
	(f) Zeng F.-L.; Xie K.-C.; Liu Y.-T.; Wang H.; Yin P.-C.; Qu L.-B.; Chen X.-L.; Yu B. Green Chem. 2022, 24, 1732. doi: 10.1039/D1GC04218A
	(g) Lu Y.-H.; Mu S.-Y.; Li H.-X.; Jiang J.; Wu C.; Zhou M.-H.; Ouyang W.-T.; He W.-M. Green Chem. 2023, 25, 5539. doi: 10.1039/D2GC04906F
	(h) Lu Y.-H.; Wu C.; Hou J.-C.; Wu Z.-L.; Zhou M.-H.; Huang X.-J.; He W.-M. ACS Catal. 2023, 13, 13071. doi: 10.1021/acscatal.3c02268
	(i) Song H.-Y.; Jiang J.; Song Y.-H.; Zhou M.-H.; Wu C.; Chen X.; He W.-M. Chin. Chem. Lett. 2024, 35, 109246. doi: 10.1016/j.cclet.2023.109246
	(j) Wu C.; Wu S.; Huang Q.; Sun K.; Huang X.; Wang J.; Yu B. Chin. Chem. Lett. 2024, 35, 110250.
	(k) He L.; Xia W.; Zhou Y.; Zhou X. Chin. J. Org. Chem. 2024, 44, 997 (in Chinese). doi: 10.6023/cjoc202310027
	(何蔺恒, 夏稳, 周玉祥, 于贤勇, 有机化学, 2024, 44, 997 ) doi: 10.6023/cjoc202310027
	(l) Zhang S.; Zhang J.; Ling X.; Zhao Y.; Ma Y.; Sun P. Chin. J. Chem. 2024, 42, 1481. doi: 10.1002/cjoc.v42.13
	(m) Zhang J.; Li X.; Chen G.; Liu H.; Luo H. Chem. Commun. 2025, 61, 1669. doi: 10.1039/D4CC05582A
	(n) Hu X.; Sun R.; Tian Y.; Xu X.; Zhu Y.; Liu H.; Liu D.; Zhang L. Adv. Synth. Catal. 2025, 367, e202401430. doi: 10.1002/adsc.v367.7
	(o) Liu J.; Li X.; Chen G.; Luo H. Adv. Synth. Catal. 2025, 367, e202500002. doi: 10.1002/adsc.v367.11
	(p) Wang Y.; Zhang J.; Wang Y.; Cao B.; Wang X.; Shen J.; Gao Y.; Li W. Chin. J. Org. Chem. 2025, 45, 3797 (in Chinese). doi: 10.6023/cjoc202504022
	(王羽欣, 张景怡, 王怡博, 曹彬烨, 王新嫦, 沈佳斌, 高一涵, 李万梅, 有机化学, 2025, 45, 3797.)
[8]	Fang L.; Yu J.; Yu Z.; Tong F.; Zhang C.; Hu D.; Zhang J.-Q.; Ren H. J. Org. Chem. 2023, 88, 17249. doi: 10.1021/acs.joc.3c02088
[9]	(a) Song H.-Y.; Xiao F.; Jiang J.; Wu C.; Ji H.-T.; Lu Y.-H.; Wang K.-L.; He W.-M. Chin. Chem. Lett. 2023, 34, 108509. doi: 10.1016/j.cclet.2023.108509 pmid: 39648635
	(b) Wang J.; Li F.; Liu K.; Li C.; Cao S.; Wu Y.; Yuan Y.; Teng F.; Wang T.; Zhou Y. Green Synth. Catal. 2024, 5, 315. pmid: 39648635
	(c) Zhou B.; Dong M.; Wang W.; Yu S.; Yue H.; Wei W.; Yi D. J. Org. Chem. 2024, 89, 18337. doi: 10.1021/acs.joc.4c02205 pmid: 39648635
[10]	(a) Zhang J.; Li X.; Liao L.; Liu H.; Luo H. Adv. Synth. Catal. 2023, 365, 4544. doi: 10.1002/adsc.v365.24
	(b) Zhou Y.; Cui Y.; Huang H.; Zhang J.‐Q.; Xu Y.; Ren H.; Dong Z.-B. Eur. J. Org. Chem. 2024, 27, e202301102.
[11]	Barsukova T.; Sato T.; Takumi H.; Niwayama S. RSC Adv. 2022, 12, 25669. doi: 10.1039/d2ra04419f pmid: 36199299
[12]	Nawrat C. C.; Jamison C. R.; Slutskyy Y.; MacMillan D. W. C.; Overman L. E. J. Am. Chem. Soc. 2015, 137, 11270. doi: 10.1021/jacs.5b07678
[13]	For selected examples about reaction of monoalkyl oxalates, see:
	(a) Zhang X.-Y.; Weng W.-Z.; Liang H.; Yang H.; Zhang B. Org. Lett. 2018, 20, 4686. doi: 10.1021/acs.orglett.8b02016
	(b) Gonzalez-Esguevillas M.; Miro J.; Jeffrey J. L.; MacMillan D. W. C. Tetrahedron 2019, 75, 4222. doi: 10.1016/j.tet.2019.05.043
	(c) Xu F.; Lai X.-L.; Xu H.-C. Synlett 2021, 32, 369. doi: 10.1055/a-1296-8652
	(d) Wang J.-X.; Ge W.; Fu M.-C.; Fu Y. Org. Lett. 2022, 24, 1471. doi: 10.1021/acs.orglett.1c04359
	(e) Xu J.; Zhao C.; Cheng D.; Xu X. Adv. Synth. Catal., 2023, 365, 4527. doi: 10.1002/adsc.v365.24
[14]	Zhang X.; MacMillan D. W. C. J. Am. Chem. Soc. 2016, 138, 13862. doi: 10.1021/jacs.6b09533
[15]	Dong J.; Wang Z.; Wang X.; Song H.; Liu Y.; Wang Q. J. Org. Chem. 2019, 84, 7532. doi: 10.1021/acs.joc.9b00972
[16]	Liu C.; Lin X.; An D.; Wang X.; Gao Q. Org. Chem. Front. 2024, 11, 358. doi: 10.1039/D3QO01742G
[17]	For some selected reviews and examples about the silver catalyzed reaction, see: (a) Li C.-J.; Bi X.; Zanoni G.; Liu Q.; Bi X. Silver Catalysis in Organic Synthesis, Vols. 1 and 2, Wiley-VCH Verlag GmbH & Co. KGaA, 2019.
	(b) Dai J.; Wang G.; Xu X.; Xu H. Chin. J. Org. Chem. 2013, 33, 2460 (in Chinese). doi: 10.6023/cjoc201307014
	(戴建军, 王光祖, 徐小岚, 许华建, 有机化学, 2013, 33, 2460.) doi: 10.6023/cjoc201307014
	(c) Fang G.; Cong X.; Zanoni G.; Liu Q.; Bi X. Adv. Synth. Catal. 2017, 359, 1422. doi: 10.1002/adsc.v359.9
	(d) Yin X.; Li W.; Zhao B.; Cheng K. Chin. J. Org. Chem. 2018, 38, 2879 (in Chinese). doi: 10.6023/cjoc201805013
	(殷晓婷, 李文炅, 赵保丽, 程凯, 有机化学, 2018, 38, 2879.) doi: 10.6023/cjoc201805013
	(e) Wang C.; Qiu G.; Li C.; Sun K.; Wang Z.; Wang X. Adv. Synth. Catal. 2022, 364, 3756. doi: 10.1002/adsc.v364.22
	(f) Wang J.; Kong W.-G.; Li F.; Liu J.; Shen Q.; Liu L.; Zhao W.-X. Org. Biomol. Chem. 2015, 13, 5399. doi: 10.1039/C5OB00438A
	(g) Zhu Y.; Wen X.; Song S.; Jiao N. ACS Catal. 2016, 6, 6465. doi: 10.1021/acscatal.6b02074
	(h) Ning Y.; Ji Q.; Liao P.; Anderson E. A.; Bi X. Angew. Chem., Int. Ed. 2017, 56, 13805. doi: 10.1002/anie.v56.44
	(i) Hu H.; Chen X.; Sun K.; Wang J.; Liu Y.; Liu H.; Yu B.; Sun Y.; Qu L.; Zhao Y. Org. Chem. Front. 2018, 5, 2925. doi: 10.1039/C8QO00882E
	(j) Yi F.; Zhao W.; Wang Z.; Bi X. Org. Lett. 2019, 21, 3158. doi: 10.1021/acs.orglett.9b00860
	(k) Ning Y.; Mekareeya A.; Babu K. R.; Anderson E. A.; Bi X. ACS Catal. 2019, 9, 4203. doi: 10.1021/acscatal.9b00500
	(l) Sun K.; Li S.-J.; Chen X.-L.; Liu Y.; Huang X.-Q.; Wei D.-H.; Qu L.-B.; Zhao Y.-F.; Yu B. Chem. Commun. 2019, 55, 2861. doi: 10.1039/C8CC10243K
	(m) Guo J.-Y.; Guan T.; Tao J.-Y.; Zhao K.; Loh T.-P. Org. Lett. 2019, 21, 8395. doi: 10.1021/acs.orglett.9b03169
	(n) Zhao F.; Guo S.; Zhang Y.; Sun T.; Yang B.; Ye Y.; Sun K. Org. Chem. Front. 2021, 8, 6895. doi: 10.1039/D1QO01425K
	(o) Liu B.; Song Q.; Liu Z.; Wang Z. Adv. Synth. Catal. 2021, 363, 3214. doi: 10.1002/adsc.v363.13
	(p) Liu B.; Wang Z.; Sun K.; Tang S.; Wang X. Chin. J. Org. Chem. 2022, 42, 1387 (in Chinese).
	(刘冰, 王智传, 孙凯, 唐石, 王薪, 有机化学, 2022, 42, 1387.) doi: 10.6023/cjoc202203053
	(q) Cui W.; Li Y.; Li X.; Li J.; Song X.; Lv J.; Jiang Y.-Y.; Yang D. Chin. Chem. Lett. 2023, 34, 107477. doi: 10.1016/j.cclet.2022.04.075
	(r) Deng Z.; Meng L.; Bing X.; Niu S.; Zhang X.; Peng J.; Luan Y.-X.; Chen L.; Tang P. J. Am. Chem. Soc. 2024, 146, 2325. doi: 10.1021/jacs.3c11653
	(s) Wang J.; Qin Y.; Cui K.; Li X.; Cui M.; Cao S.; Zhang L.; Shen Q.; Wang T.; Li F. Chem. Commun. 2025, 61, 3359. doi: 10.1039/D4CC05675B
[18]	(a) Litvinas N. D.; Brodsky B. H.; Bois J. D. Angew. Chem., Int. Ed. 2009, 48, 4513. doi: 10.1002/anie.v48:25
	(b) Yu H.; Zhang L.; Yang Z.; Li Z.; Zhao Y.; Xiao Y.; Guo H. J. Org. Chem. 2013, 78, 8427. doi: 10.1021/jo401107v

Entry	Catalyst	Additive	Solvent (V∶V=1∶1)	T/℃	Yield^b/%
1	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	25	Trace
2	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	45	56
3	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	60	72
4	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	80	70
5	AgOAc	K₂S₂O₈	CH₃CN/H₂O	60	67
6	AgF	K₂S₂O₈	CH₃CN/H₂O	60	64
7	AgNO₃	Na₂S₂O₈	CH₃CN/H₂O	60	69
8	AgNO₃	(NH₄)₂S₂O₈	CH₃CN/H₂O	60	63
9	AgNO₃	K₂S₂O₈	Acetone/H₂O	60	36
10	AgNO₃	K₂S₂O₈	DMSO/H₂O	60	58
11^c	AgNO₃	K₂S₂O₈	DMSO/H₂O	60	61
12	AgNO₃	—	CH₃CN/H₂O	60	Trace
13	—	K₂S₂O₈	CH₃CN/H₂O	60	n.d.

Entry	Catalyst	Additive	Solvent (V∶V=1∶1)	T/℃	Yield^b/%
1	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	25	Trace
2	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	45	56
3	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	60	72
4	AgNO₃	K₂S₂O₈	CH₃CN/H₂O	80	70
5	AgOAc	K₂S₂O₈	CH₃CN/H₂O	60	67
6	AgF	K₂S₂O₈	CH₃CN/H₂O	60	64
7	AgNO₃	Na₂S₂O₈	CH₃CN/H₂O	60	69
8	AgNO₃	(NH₄)₂S₂O₈	CH₃CN/H₂O	60	63
9	AgNO₃	K₂S₂O₈	Acetone/H₂O	60	36
10	AgNO₃	K₂S₂O₈	DMSO/H₂O	60	58
11^c	AgNO₃	K₂S₂O₈	DMSO/H₂O	60	61
12	AgNO₃	—	CH₃CN/H₂O	60	Trace
13	—	K₂S₂O₈	CH₃CN/H₂O	60	n.d.