Recent Progress in Gold-Catalyzed Intramolecular Cyclization of Alkynes and Its Applications

doi:10.6023/cjoc202407034

Abstract

As gold catalysts have the advantages of high reactivity, unique selectivity, and high affinity for π bonds, they are usually used to activate alkynes, alkenes, and allenes. Gold catalysts not only promote the activation of alkynes to form vinyl gold intermediates or gold carbene intermediates to participate in the reaction, but also catalyze the intramolecular cyclization to form new types of heterocycles or polycyclic compounds. This review summarizes the gold-catalyzed intramolecular cyclization of alkynes in recent eight years, including the intramolecular cyclization of different nucleophilic carbon-atom and heteroatoms, and its applications in the total synthesis of natural products.

Key words: gold catalysis, alkynes, intramolecular cyclization, heterocyclic compounds, reaction selectivity

Cite this article

Xu Zhang, Peisen Zou, Xiaoqing Liu, Hongyan Bi, Dongliang Mo. Recent Progress in Gold-Catalyzed Intramolecular Cyclization of Alkynes and Its Applications[J]. Chinese Journal of Organic Chemistry, 2025, 45(10): 3755-3776.

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Fig. & Tab. 48

Figure 1. Gold-catalyzed intramolecular cyclization of alkynes

Scheme 1. Gold-catalyzed intramolecular dearomatization of naphthols

Scheme 2. Gold-catalyzed cyclization of 1,6-diynyl dithioacetals

Scheme 3. Gold(I)-catalyzed intramolecular hydroarylation of methylenecyclopropanes

Scheme 4. Gold-catalyzed cyclization to synthesize benzo[a]fluorene derivatives

Scheme 5. Gold-catalyzed intramolecular cyclization to synthesize 1,2-dihydro[c][2,7]naphthyridine derivatives

Scheme 6. Gold-catalyzed cyclization of 1,5-diynes

Scheme 7. Gold-catalyzed cyclization to synthesize indeno[1,2-c] pyrroles

Scheme 8. Gold-catalyzed cyclization to synthesize aza-aromatic compounds

Scheme 9. Gold-catalyzed cyclization to synthesize benzo[c,d]indole derivatives

Scheme 10. Gold(I)-catalyzed bis-cyclization of allenynes

Scheme 11. Gold-catalyzed carboxyalkylation of internal alkynes

Scheme 12. Gold-catalyzed intramolecular hydroalkylation to synthesize indenes

Scheme 13. Gold-catalyzed selective synthesis of indolyl-ynones to prepare carbazoles

Scheme 14. Gold(I)-catalyzed regioselective cyclizations of N-propargyl tryptamines to synthesize spiroindoleni

Scheme 15. Gold-catalyzed selective cyclization of alkynyl-tethered indoles to prepare rutaecarpine derivatives

Scheme 16. Gold-catalyzed intramolecular dearomatization reactions of indoles

Scheme 17. Gold-catalyzed dearomatization spirocyclization reactions of N-propargyl tryptamines

Scheme 18. Gold(I)-catalyzed selective cyclization to prepare pseudorutaecarpine derivatives

Scheme 19. Gold(I)-catalyzed dearomatization/cyclization of 1,6-diyne

Scheme 20. Possible mechanism of gold(I)-catalyzed dearomatization of 1,6-diyne compounds

Scheme 21. Gold-catalyzed cycloisomerization/ring expansion of alkynyl spiro-epoxyoxindoles

Scheme 22. Gold(I)-catalyzed intramolecular hydroarylation of alkynylindoles

Scheme 23. Gold(III)/Yb(III)-catalyzed synthesis of chiral dihydrocarbazoles in one pot reaction

Scheme 24. Gold-catalyzed selective cyclization of furanyl-alkynes

Scheme 25. Gold (III)-catalyzed selective cyclization of alkynyl quinazolinone-tethered pyrroles

Scheme 26. Gold-catalyzed cyclization to synthesize indenone derivatives

Scheme 27. Gold-catalyzed carboalkoxylation of ynamides

Scheme 28. Gold-catalyzed spirocyclization of furan-ynones

Scheme 29. Gold-catalyzed asymmetric hydroarylation of furan-ynones

Scheme 30. Gold(I)-catalyzed atroposelective synthesis of 1,1'-binaphthalene-2,3'-diols

Scheme 31. Gold(I)-catalyzed asymmetric hydroarylation of ortho-alkynylaryl ferrocenes derivatives

Scheme 32. Gold-catalyzed cyclization of 1-(2′-azidoaryl) propynols

Scheme 33. Gold-catalyzed of hydroaminations

Scheme 34. Gold-catalyzed regioselective synthesis of pyrazolo[1,4]oxazepines

Scheme 35. Gold-catalyzed asymmetric to synthesize 3-pyrroline compounds

Scheme 36. Gold-catalyzed cyclization of diarylthiooximines

Scheme 37. Gold-catalyzed cyclization of alkynediols

Scheme 38. Gold-catalyzed rearrangement/cyclization to synthesize 2,5-dihydrofurans

Scheme 39. Gold/Iridium catalyzed alkynylamide cyclization/asymmetric allylic alkylation cascade reaction

Scheme 40. Application of gold-catalyzed cyclization in the total synthesis of citreoviranol (1)

Scheme 41. Application of gold-catalyzed cyclization in the total synthesis of (±)-Strictamine

Scheme 42. The application of gold-catalyzed cyclization in the synthesis of tricyclic indolines

Scheme 43. Application of gold-catalyzed cyclization in the total synthesis of orientalol F

Scheme 44. Application of gold-catalyzed cyclization in the total synthesis of (＋)-strictamine

Scheme 45. Application of gold-catalyzed cyclization in the total synthesis of ()-aspidophylline A

Scheme 46. Application of gold-catalyzed cyclization in the total synthesis of Vindorosine

Scheme 47. Application of gold-catalyzed cyclization in the synthesis of dideoxy sugar

References 53

[1]	(a) Hashmi, A. S. K. Chem. Rev. 2007, 107, 3180. pmid: 21391565
	(b) Fürstner, A. Chem. Soc. Rev. 2009, 38, 3208. doi: 10.1039/b816696j pmid: 21391565
	(c) Cossy, J. Pure Appl. Chem. 2010, 82, 1365. pmid: 21391565
	(d) Corma, A.; Leyva-Pérez, A.; Sabater, M. J. Chem. Rev. 2011, 111, 1657. doi: 10.1021/cr100414u pmid: 21391565
[2]	(a) Pyykkö, P. Angew. Chem., Int. Ed. 2002, 41, 3573.
	(b) Schwartz, H. Angew. Chem., Int. Ed. 2003, 42, 4442.
	(c) Pyykkö, P. Angew. Chem., Int. Ed. 2004, 43, 4412.
	(d) Gorin, D. J.; Toste, F. D. Nature 2007, 446, 395.
	(e) Jimenez-Núñez, E.; Echavarren, A. M. Chem. Rev. 2008, 108, 3326.
[3]	Rocchigiani, L.; Bochmann, M. Chem. Rev. 2021, 121, 8364.
[4]	(a) Liu, X.-Q.; Chen, Y.-J.; Zou, P.-S.; Su, J.-C.; Pan, C.-X.; Mo, D.-L.; Su, G.-F. Chem.-Eur. J. 2024, 30, e202402085. pmid: 22238519
	(b) Borsini, E.; Broggini, G.; Fasana, A.; Baldassarri, C.; Manzo, A. M.; Perboni, A. D. Beilstein J. Org. Chem. 2011, 7, 1468. doi: 10.3762/bjoc.7.170 pmid: 22238519
	(c) Liu, Y.; Xu, W.; Wang, X. Org. Lett. 2010, 12, 1448. pmid: 22238519
	(d) Kong, X.-F.; Guo, X.-Y.; Gu, Z.-Y.; Wei, L.-S.; Liu, L.-L.; Mo, D.-L.; Pan, C.-X.; Su, G.-F. Org. Chem. Front. 2020, 7, 2055. pmid: 22238519
	(e) Modha, S. G.; Kumar, A.; Vachhani, D. D.; Sharma, S. K.; Parmar, V. S.; Van der Eycken, E. V. Chem. Commun. 2012, 48, 10916. pmid: 22238519
[5]	(a) Cheng, J.-S.; Jiang, H.-F.; Zhang, Q.-J.; Ouyang, X.-Y. Chin. J. Org. Chem. 2003, 23, 313 (in Chinese). pmid: 21487625
	(程金生, 江焕峰, 张群健, 欧阳小月, 有机化学, 2003, 23, 313.) pmid: 21487625
	(b) Alcaide, B.; Almendros, P.; Alonso, J. M. Org. Biomol. Chem. 2011, 9, 4405. doi: 10.1039/c1ob05249g pmid: 21487625
	(c) Obradors, C.; Echavarren, A. M. Acc. Chem. Res. 2014, 47, 902. pmid: 21487625
	(d) Liao, Y.; Zhu, L.; Yu, Y.; Chen, G.; Huang, X. Chin. J. Org. Chem. 2017, 37, 2785 (in Chinese). pmid: 21487625
	(廖云, 朱磊, 俞颖华, 陈贵, 黄学良, 有机化学, 2017, 37, 2785.) pmid: 21487625
[6]	Wu, W.-T.; Xu, R.-Q.; Zhang, L.; You, S.-L. Chem. Sci. 2016, 7, 3427.
[7]	Xu, W.; Chen, M.; Sun, N.; Liu, Y. Chem. Commun. 2016, 52, 11000.
[8]	Fang, W.; Tang, X.-Y.; Shi, M. RSC Adv. 2016, 6, 40474.
[9]	Fang, W.; Wei, Y.; Shi, M. Chem. Commun. 2017, 53, 11666.
[10]	Goutham, K.; Kadiyala, V.; Sridhar, B.; Karunakar, G. V. Org. Biomol. Chem. 2017, 15, 7813.
[11]	Wurm, T.; Bucher, J.; Rudolph, M.; Rominger, F.; Hashmi, A. S. K. Adv. Synth. Catal. 2017, 359, 1637.
[12]	Shen, W.-B.; Zhou, B.; Zhang, Z.-X.; Yuan, H.; Fang, W.; Ye, L.-W. Org. Chem. Front. 2018, 5, 2468.
[13]	Zhao, Q.; Rayo, D. F. L.; Campeau, D.; Daenen, M.; Gagosz, F. Angew. Chem., Int. Ed. 2018, 57, 13603.
[14]	Komatsu, H.; Ikeuchi, T.; Tsuno, H.; Arichi, N.; Yasui, K.; Oishi, S.; Inuki, S.; Fukazawa, A.; Ohno, H. Angew. Chem., Int. Ed. 2021, 60, 27019.
[15]	Tsuno, H.; Shen, J.; Komatsu, H.; Arichi, N.; Inuki, S.; Ohno, H. Angew. Chem., Int. Ed. 2023,62, e202307532.
[16]	He, J.; Cao, T.; Chen, K.; Zhu, S. Org. Lett. 2024, 26, 2596.
[17]	Thilmany, P.; Guarnieri-Ibánez, A.; Jacob, C.; Lacour, J.; Evano, G. ACS Org. Inorg. Au 2022, 2, 53. doi: 10.1021/acsorginorgau.1c00021 pmid: 36855401
[18]	Liddon, J. T. R.; James, M. J.; Clarke, A. K.; O'Brien, P.; Taylor, R. J. K.; Unsworth, W. P. Chem.-Eur. J. 2016, 22, 8777. doi: 10.1002/chem.201601836 pmid: 27124236
[19]	Magné, V.; Marinetti, A.; Gandon, V.; Voituriez, A.; Guinchard, X. Adv. Synth. Catal. 2017, 359, 4036.
[20]	Kong, X.-F.; Zhan, F.; He, G.-X.; Pan, C.-X.; Gu, C.-X.; Lu, K.; Mo, D.-L.; Su, G.-F. J. Org. Chem. 2018, 83, 2006.
[21]	Wu, W.-T.; Ding, L.; Zhang, L.; You, S.-L. Org. Lett. 2020, 22, 1233.
[22]	Sabat, N.; Soualmia, F.; Retailleau, P.; Benjdia, A.; Berteau, O.; Guinchard, X. Org. Lett. 2020, 22, 4344.
[23]	Wang, W.; Chen, N.-Y.; Zou, P.-S.; Pang, L.; Mo, D.-L.; Pan, C.-X.; Su, G.-F. Adv. Synth. Catal. 2022, 364, 787.
[24]	Chen, G.; Liu, P.; Zou, H.; Hu, J.; Fang, X.; Xu, D.; He, Y.; Wei, H.; Xie, W. Org. Lett. 2021, 23, 2279.
[25]	Xiao, J.-A; Peng, H.; Liang, J.-S.; Luo, X.-Y.; Cheng, X.-L.; Su, W. Asian J. Org. Chem. 2021, 10, 1436.
[26]	Yang, J.-M.; Yao, M.-L.; Li, J.-C.; Liu, J.-K.; Wu, B. Org. Lett. 2022, 24, 6505.
[27]	Wang, X.; Zhou, A.-H.; Hu, T.-Q.; Xu, Z.; Zhou, B.; Ye, L.-W. Org. Lett. 2024, 26, 2051.
[28]	Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. Rev. 1996, 96, 635. pmid: 11848768
[29]	Patil, N. T.; Yamamoto, Y. Chem. Rev. 2008, 108, 3395.
[30]	Sun, N.; Xie, X.; Chen, H.; Liu, Y. Chem.-Eur. J. 2016, 22, 14175.
[31]	Wei, L.-S.; He, G.-X.; Kong, X.-F.; Pan, C.-X.; Mo, D.-L.; Su, G.-F. J. Org. Chem. 2018, 83, 6719.
[32]	Yamada, T.; Park, K.; Tachikawa, T.; Fujii, A.; Rudolph, M.; Hash-mi, A. S. K.; Sajiki, H. Org. Lett. 2020, 22, 1883.
[33]	Qi, L.-J.; Shi, C.-Y.; Chen, P.-F.; Li, L.; Fang, G.; Qian, P.-C.; Deng, C.; Zhou, J.-M.; Ye, L.-W. ACS Catal. 2021, 11, 3679.
[34]	Chen, Y.; Xu, W.; Xie, X.; Pei, M.; Lu, M.; Wang, Y.; Liu, Y. Org. Lett. 2021, 23, 1090.
[35]	Satoh, M.; Shibata, Y.; Kimura, Y.; Tanaka, K. Eur. J. Org. Chem. 2016, 26, 4465.
[36]	Zhang, J.; Simon, M.; Golz, C.; Alcarazo, M. Angew. Chem., Int. Ed. 2020, 59, 5647.
[37]	Zhang, P.-C.; Li, Y.-L.; He, J.; Wu, H.-H.; Li, Z.; Zhang, J. Nat. Commun. 2021, 12, 4609.
[38]	Wu, X.; Zheng, L.-L.; Zhao, L.-P.; Zhu, C.-F.; Li, Y.-G. Chem. Commun. 2019, 55, 14769.
[39]	Veguillas, M.; Rosair, G. M.; Bebbington, M. W. P.; Lee, A.-L. ACS Catal. 2019, 9, 2552. doi: 10.1021/acscatal.9b00249
[40]	Thummala, Y.; Raju, C. E.; Purnachandar, D.; Sreenivasulu, G.; Doddi, V. R.; Karunakar, G. V. Eur. J. Org. Chem. 2020, 2020, 3560.
[41]	Cheng, X.; Zhang, L. Org. Lett. 2021, 23, 8194.
[42]	Mackenroth, A.V.; Antoni, P. W.; Rominger, F.; Rudolph, M.; Hashmi, A. S. K. Org. Lett. 2023, 25, 2907. doi: 10.1021/acs.orglett.3c00953 pmid: 37071638
[43]	Fu, J.; Gu, Y.; Yuan, H.; Luo, T.; Liu, S.; Lan, Y.; Gong, J.; Yang, Z. Nat. Commun. 2015, 6, 8617.
[44]	Sunil, K.; Thummala, Y.; Dalovai, P.; Balasubramanian, S.; Karunakar, G. V. Org. Biomol. Chem. 2019, 17, 6015.
[45]	Wang, R.-X.; Zhao, Q.-R.; Gu, Q.; You, S.-L. Acta Chim. Sinica 2023, 81, 431 (in Chinese).
	(王瑞祥, 赵庆如, 顾庆, 游书力, 化学学报, 2023, 81, 431.)
[46]	Quach, R; Furkert, D. P.; Brimble, M. A. J. Org. Chem. 2016, 81, 8343.
[47]	Nishiyama, D.; Ohara, A.; Chiba, H.; Kumagai, H.; Oishi, S.; Fujii, N.; Ohno, H. Org. Lett. 2016, 18, 1670. doi: 10.1021/acs.orglett.6b00536 pmid: 27011119
[48]	He, W.; Griffiths, B. M.; Wang, W.; Wang, X. Org. Biomol. Chem. 2017, 15, 4241. doi: 10.1039/c7ob00897j pmid: 28466945
[49]	Gu, Y.; Huang, J.; Gong, J.; Yang, Z. Org. Chem. Front. 2017, 4, 2296.
[50]	Smith, M. W.; Zhou, Z.; Gao, A. X.; Shimbayashi, T.; Snyder, S. A. Org. Lett. 2017, 19, 1004.
[51]	Wang, T.; Duan, X.; Zhao, H.; Zhai, S.; Tao, C.; Wang, H.; Li, Y.; Cheng, B.; Zhai, H. Org. Lett. 2017, 19, 1650.
[52]	Matsuoka, J.; Kumagai, H.; Inuki, S.; Oishi, S.; Ohno, H. J. Org. Chem. 2019, 84, 9358. doi: 10.1021/acs.joc.9b01149 pmid: 31244165
[53]	Yalamanchili, S.; Miller, W.; Chen, X.; Bennett, C. S. Org. Lett. 2019, 21, 9646. doi: 10.1021/acs.orglett.9b03812 pmid: 31755271

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