钯催化1,6-烯炔的环化反应研究

doi:10.6023/cjoc202401032

摘要/Abstract

官能化的碳环或杂环结构广泛存在于天然产物及其他生物活性分子中, 是一类极具合成价值的重要骨架. 而1,n-烯炔的环化反应是构建官能化的碳环或杂环化合物的最具原子经济性, 且高效的方法之一, 其中钯催化的1,6-烯炔的环化反应研究较为成熟, 取得了一系列重要进展. 聚焦于由炔烃亲核钯化启动的1,6-烯炔的环化反应, 按照炔烃的亲核钯化方式包括氢钯化、碳钯化、卤钯化和氧钯化等分类, 系统介绍了近二十年内钯催化1,6-烯炔的环化反应进展, 尤其是不对称催化反应, 探讨了反应的机理, 并展望了该领域今后发展的方向.

关键词: 钯催化, 1,6-烯炔, 环化反应, 亲核钯化, 碳环化合物, 杂环化合物

Functionalized carbo- and hetero-cyclic compounds are widely found in natural products and other bioactive molecules, which are also important scaffolds with significant synthetic value. The cyclization of 1,n-enynes is one of the most atom-economic and efficient approaches. In particular, the palladium-catalyzed cyclization of 1,6-enynes has been extensively studied and has achieved significant advancements. This review focuses on the cyclization of 1,6-enynes initiated by nucleopalladation of alkynes, including hydropalladation, carbopalladation, halopalladation and oxypalladation. It was classified by the nucleopalladation and the recent developments in palladium-catalyzed 1,6-enyne cyclization over the past two decades are systematically summarized. Special emphasis is placed on the asymmetric reactions, and reaction mechanisms, along with further prospects of this field.

Key words: palladium catalysis, 1,6-enynes, cyclization reaction, nucleopalladation, carbocyclic compounds, heterocyclic compounds

引用此文

刘雯娟, 陈品红. 钯催化1,6-烯炔的环化反应研究[J]. 有机化学, 2024, 44(7): 2077-2091.

Wenjuan Liu, Pinhong Chen. Palladium-Catalyzed Cyclization of 1,6-Enynes[J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2077-2091.

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图/表 38

图式1. 钯催化的1,6-烯炔的环异构化反应

Scheme 1. Pd-catalyzed cycloisomerization of 1,6-enynes

图式2. 钯催化1,n-烯炔环化反应的启动方式

Scheme 2. Initial pathways of Pd-catalyzed cyclization of 1,n- enynes

图式3. 钯催化1,6-烯炔环化反应合成1,3-二烯产物

Scheme 3. Pd-catalyzed cyclization of 1,6-enynes for the synthesis of 1,3-dienes

图式4. 钯催化1,6-烯炔环化反应合成γ,δ-不饱和羰基化合物

Scheme 4. Pd-catalyzed cyclization of 1,6-enynes for the synthesis of γ,δ-unsaturated carbonyl compounds

图式5. 基于双膦配体的钯催化1,6-烯炔不对称环化反应

Scheme 5. Pd-catalyzed enantioselective cyclization of 1,6- enynes with chiral diphosphine ligands

图式6. 基于氮膦配体的钯催化1,6-烯炔不对称环化反应

Scheme 6. Pd-catalyzed enantioselective cyclization of 1,6- enynes with chiral N,P ligands

图式7. 钯催化1,6-烯炔的不对称氢酯化环化反应

Scheme 7. Pd-catalyzed enantioselective hydroesterificative cyclization of 1,6-enynes

图式8. 钯催化1,6-烯炔的硼化环化反应

Scheme 8. Pd-catalyzed borylative cyclization of 1,6-enynes

图式9. 钯催化1,6-烯炔的卤化环化反应

Scheme 9. Pd-catalyzed halogenative cyclization of 1,6-enynes

图式10. 阳离子钯催化1,6-烯炔的还原环化反应

Scheme 10. Cationic Pd-catalyzed reducitve cyclization of 1,6-enynes

图式11. 钯催化1,6-烯炔的endo型环化反应

Scheme 11. Pd-catalyzed endo-cyclization of 1,6-enynes

图式12. 钯催化1,6-烯炔的endo型环化反应

Scheme 12. Pd-catalyzed endo-cyclization of 1,6-enynes

图式13. 钯催化含烯丙基氯的1,6-烯炔的芳基环化反应

Scheme 13. Pd-catalyzed arylcyclization of 1,6-enynes bearing allyl chloride

图式14. 钯催化1,6-烯炔的芳基环化反应合成吡咯

Scheme 14. Pd-catalyzed arylcyclization of 1,6-enynes for the synthesis of pyrroles

图式15. 钯催化1,6-烯炔的不对称芳基环化反应

Scheme 15. Pd-catalyzed enantioselective arylcyclization of 1,6-enynes

图式16. 钯催化1,6-烯炔的芳基环化反应

Scheme 16. Pd-catalyzed arylcyclization of 1,6-enynes

图式17. 钯催化1,6-烯炔的双芳基环化反应

Scheme 17. Pd-catalyzed diarylating carbocyclization of 1,6- enynes

图式18. 钯催化1,6-烯炔的卤化环化反应中的卤离子效应

Scheme 18. Halide effect in Pd-catalyzed halogenative cyclization of 1,6-enynes

图式19. 钯催化1,6-烯炔的卤化环化反应

Scheme 19. Pd-catalyzed halogenative cyclization of 1,6-enynes

图式20. 经历顺式氯钯化的1,6-烯炔的卤化环化反应

Scheme 20. Pd-catalyzed halogenative cyclization of 1,6-enynes via cis-chloropalladation

图式21. 双氧水为氧化剂的钯催化1,6-烯炔的氯化环化反应

Scheme 21. Pd-catalyzed chlorocyclization of 1,6-enynes with H2O2 as the oxidant

图式22. 钯催化1,6-烯炔的氟化环化反应

Scheme 22. Pd-catalyzed fluorocyclization of 1,6-enynes

图式23. 钯催化1,6-烯炔的对映选择性氯化环化反应

Scheme 23. Pd-catalyzed enantioselective chlorocyclization of 1,6-enynes

图式24. 钯催化1,6-烯炔的对映选择性氧化环化反应

Scheme 24. Pd-catalyzed enantioselective acetoxylcyclization of 1,6-enynes

图式25. 钯催化1,6-烯炔的氧化环化反应中双氮配体作用

Scheme 25. Ligand effect in Pd-catalyzed acetoxylcyclization of 1,6-enynes

图式26. 手性异噁唑啉配体促进的钯催化1,6-烯炔的对映选择性氧化环化反应

Scheme 26. Pd-catalyzed enantioselective acetoxylcyclization of 1,6-enynes with chiral spiro bis(isoxazoline) (SPRIX) ligand

图式27. 钯催化1,6-不饱和烯炔的氧化环化反应

Scheme 27. Pd-catalyzed acetoxylcyclization of 1,6-enynes

图式28. 钯催化含环己二烯酮1,6-烯炔的对映选择性氧化环化反应

Scheme 28. Pd-catalyzed enantioselective acetoxylcyclization of 1,6-enynes with cyclohexadienones

图式29. 钯催化1,6-烯炔的串联环化反应

Scheme 29. Pd-catalyzed cascade cyclization of 1,6-enynes

图式30. 钯催化1,6-烯炔的串联环化反应机理

Scheme 30. Mechanism of Pd-catalyzed cascade cyclization of 1,6-enynes

图式31. 钯催化缺电子1,6-烯炔的串联环化反应

Scheme 31. Pd-catalyzed cascade cyclization of electron deficient 1,6-enynes

图式32. 钯催化1,6-烯炔的对映选择性串联环化反应

Scheme 32. Pd-catalyzed enantioselective cascade cyclization of 1,6-enynes

图式33. 钯催化1,6-烯炔的[3+2]环化反应

Scheme 33. Pd-catalyzed [3+2] cyclization of 1,6-enynes

图式34. 钯催化1,6-烯炔的[3+2]环化反应机理

Scheme 34. Mechanism of Pd-catalyzed [3+2] cyclization of 1,6-enynes

图式35. 钯催化1,6-烯炔的分子内串联环化反应

Scheme 35. Pd-catalyzed intramolecular cascade cyclization of 1,6-enynes

图式36. 水作为氧亲核试剂的钯催化1,6-烯炔的串联环化反应

Scheme 36. Pd-catalyze Pd-catalyzed cascade cyclization of 1,6-enynes with H2O as the oxygen nucleophiles

图式37. 胺作为亲核试剂的钯催化1,6-烯炔的串联环化反应

Scheme 37. Pd-catalyzed cascade cyclization of 1,6-enynes with amides as nucleophiles

图式38. 硫氰作为亲核试剂的钯催化1,6-烯炔的串联环化反应

Scheme 38. Pd-catalyzed cascade cyclization of 1,6-enynes with thiocyanide as nucleophiles

参考文献 55

[1]	(a) Taylor, R. D.; MacCoss, M.; Lawson, A. D. G. J. Med. Chem. 2014, 57, 5845.
	(b) Hammder, N.; Leth, L. A.; Stiller, J.; Jensen, M. E.; Jørgensen, K. A. Chem. Sci. 2016, 7, 3649.
[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.
	(b) Chen, M.; Went, Y.; Lei, A. Prog. Chem. 2010, 22, 1341. (in Chinese)
	(陈茂, 翁玥, 雷爱文, 化学进展, 2010, 22, 1341.)
	(c) Michelet, V.; Toullec, P. Y.; Genêt, J.-P. Angew. Chem., Int. Ed. 2008, 47, 4268.
	(d) Tong, X.; Zhang, Z. Chin. J. Org. Chem. 2004, 24, 591. (in Chinese)
	(童晓峰, 张兆国, 有机化学, 2004, 24, 591.)
	(e) Aubert, C.; Buisine, O.; Malacria, M. Chem. Rev. 2002, 102, 813.
	(f) Trost, B. M. Acc. Chem. Res. 1990, 23, 34.
	(g) Hu, L.-P.; Zhang, D.-R. Huang, X.-H.; Liu, F.-L; Li, X.; Teng, M.-Y.; Huang, G.-L. Chin. J. Chem. 2022, 40, 2756.
	(h) Liu, J.-X.; Xu, S.-Q.; Han, Y.-P.; Liang, Y.-M. Adv. Synth. Catal. 2024, 366, 1220.
[3]	Trost, B. M.; Lautens, M. J. Am. Chem. Soc. 1985, 107, 1781.
[4]	Takacs, J. M.; Zhu, J.; Chandramouli, S. V. J. Am. Chem. Soc. 1992, 124, 773.
[5]	Fairlamb, I. J. S. Angew. Chem., Int. Ed. 2004, 43, 1048.
[6]	Lu, X.; Zhu, G.; Wang. Z. Synlett 1998, 115.
[7]	(a) Huang, X.; Nguyen, M. H.; Pu, L.; Zhang, L.; Chi, Y. R.; Wu, Y.-D.; Zhou, J. S. Angew. Chem., Int. Ed. 2020, 59, 10814.
	(b) Li, Q.; Zhang, Y.; Liu, P.; Zhong, J.; Gong, B.; Yao, H.; Lin, A. Angew. Chem., Int. Ed. 2023, 62, e202211988.
[8]	Trost, B. M.; Romero, D. L.; Rise, F. J. Am. Chem. Soc. 1994, 116, 4268.
[9]	Trost, B. M.; Pedregal, C. J. Am. Chem. Soc. 1992, 114, 7292.
[10]	Oh, C. H.; Jung, H. H.; Kim, J. S.; Cho, S. W. Angew. Chem., Int. Ed. 2000, 39, 752. pmid: 10760858
[11]	Hatano, M.; Terada, M.; Mikami, K. Angew. Chem., Int. Ed. 2001, 40, 249.
[12]	Hatano, M.; Mikami, K. J. Am. Chem. Soc. 2003, 125, 4704.
[13]	(a) Hatano, M.; Yamanaka, M.; Mikami, K. Eur. J. Org. Chem. 2003, 2552.
	(b) Hatano, M.; Mikami, K. Org. Biomol. Chem. 2003, 1, 3871.
[14]	Quan, X.; Liu, J.; Rabten, W.; Diomedi, S.; Singh, T.; Andersson, P. G. Eur. J. Org. Chem. 2016, 3427.
[15]	Ren, X.; Tang, L.; Shen, C.; Li, H.; Wang, P.; Dong, K. Org. Lett. 2021, 23, 3561.
[16]	Marco-Martínez, J.; López-Carrillo, V.; Buñuel, E.; Simancas, R.; Cárdenas, D. J. J. Am. Chem. Soc. 2007, 129, 1874. pmid: 17260998
[17]	Sun, D.; Zhou, B.; Liu, L.; Chen, X.; Hou, H.; Han, Y.; Yan, C.; Shi, Y.; Zhu, S. Org. Lett. 2023, 25, 4677.
[18]	Jia, X.; Petrone, D. A.; Lautens, M. Angew. Chem., Int. Ed. 2012, 51, 9870.
[19]	Petrone, D. A.; Franzoni, I.; Ye, J.; Rodríguez, J. F.; Poblador- Bahamonde, A. I.; Lautens, M. J. Am. Chem. Soc. 2017, 139, 3546. doi: 10.1021/jacs.7b00482 pmid: 28195710
[20]	Wu, W.; Chen, T.; Chen, J.; Han, X. J. Org. Chem. 2017, 83, 1033.
[21]	Mikami, K.; Hatano, M. Proc. Natl. Acad. Sci. 2004, 101, 5767.
[22]	Dong, M.; Qi, L.; Qian, J.; Yu, S.; Tong, X. J. Am. Chem. Soc. 2023, 145, 1973.
[23]	(a) Kawasaki, S.; Satoh, T.; Miura, M.; Nomura, M. J. Org. Chem. 2003, 68, 6836. pmid: 12919062
	(b) Satoh, T.; Ogino, S.; Miura, M.; Nomura, M. Angew. Chem., Int. Ed. 2004, 43, 5063. pmid: 12919062
	(c) Oh, C. H.; Jung, H. H.; Kim, K. S.; Kim, N. Angew. Chem., Int. Ed. 2003, 42, 805. pmid: 12919062
	(d) For a review, see: Rajesh, M.; Kumar, G. R. Asian J. Org. Chem. 2023, 12, e202300106. pmid: 12919062
[24]	Zhu, G.; Zhang, Z. Org. Lett. 2003, 5, 3645.
[25]	Meng, T. J.; Hu, Y.; Wang, S. J. Org. Chem. 2010, 75, 582.
[26]	Meng, T.; Hu, Y.; Sun, Y.; Zhu, T.; Wang, S. Tetrahedron 2010, 66, 8648.
[27]	Shen, K.; Han, X.; Lu, X. Org. Lett. 2012, 14, 1756. doi: 10.1021/ol3003546 pmid: 22449236
[28]	Murthy, A. S.; Donikela, S.; Reddy, C. S.; Chegondi, R. J. Org. Chem. 2015, 80, 5566.
[29]	Shen, K.; Han, X.; Lu, X.; Hu, Z. Tetrahedron Lett. 2017, 58, 3768.
[30]	Jiang, M.; Jiang, T.; Bäckvall, J. E. Org. Lett. 2012, 14, 3538. doi: 10.1021/ol301551x pmid: 22716930
[31]	Kaneda, K.; Uchiyama, T.; Fujiwara, Y.; Imanaka, T.; Teranish, S. J. Org. Chem. 1979, 44, 55.
[32]	(a) Ma, S.; Lu, X. J. Chem. Soc., Chem. Commun. 1990, 733.
	(b) Ma, S.; Lu, X. J. Org. Chem. 1991, 56, 5120.
	(c) Ma, S.; Zhu, G.; Lu, X. J. Org. Chem. 1993, 58, 3692.
	(d) Ma, S.; Lu, X. J. Org. Chem. 1993, 58, 1245.
	(e) Ji, J.; Lu, X. Tetrahedron 1994, 50, 9067.
	(f) Ji, J. Zhang, C.; Lu, X. J. Org. Chem. 1995, 60, 1160.
	(g) Wang, Z.; Lu, X. Tetrahedron Lett. 1997, 38, 5213.
[33]	Xie, X.; Lu, X.; Liu, Y.; Xu, W. J. Org. Chem. 2001, 66, 6545. pmid: 11578203
[34]	Zhu, G.; Zhang, Z. J. Org. Chem. 2005, 70, 3339.
[35]	Yin, G.; Liu, G. Angew. Chem., Int. Ed. 2008, 47, 5442.
[36]	Takenaka, K.; Hashimoto, S.; Takizawa, S.; Sasai, H. Adv. Synth. Catal. 2011, 353, 1067.
[37]	Peng, H.; Liu, G. Org. Lett. 2011, 13, 772.
[38]	Tang, J.; Zhang, L.; Wu, W.; Yang, S.; Jiang, H. Chem.-Eur. J. 2022, 28, e202202528.
[39]	(a) Lu, X.; Zhu, G.; Ma, S. Tetrahedron Lett. 1992, 33, 7205.
	(b) Wakabayashi, T.; Ishii, Y.; Murata, T.; Mizobe, Y.; Hidai, M. Tetrahedron Lett. 1995, 36, 5585.
[40]	Zhang, Q.; Lu, X. J. Am. Chem. Soc. 2000, 122, 7604.
[41]	Zhang, Q.; Lu, X.; Han, X. J. Org. Chem. 2001, 66, 7676. pmid: 11701020
[42]	Song, J.; Shen, Q.; Xu, F.; Lu, X. Tetrahedron 2007, 63, 5148.
[43]	Xu, W.; Kong, A.; Lu, X. J. Org. Chem. 2006, 71, 3854.
[44]	Muthiah, C.; Arai, M. A.; Shinohara, T.; Arai, T.; Takizawa, S.; Sasai, H. Tetrahedron Lett. 2003, 44, 5201.
[45]	Zhao, L.; Lu, X.; Xu, W. J. Org. Chem. 2005, 70, 4059.
[46]	Bai, Y.-Q.; Wang, X.-W.; Wu, B.; Wang, X.-Q.; Liao, R.-Z.; Li, M.; Zhou, Y.-G. ACS Catal. 2023, 13, 9829.
[47]	Welbes, L. L.; Lyons, T. W.; Cychosz, K. A.; Sanford, M. S. J. Am. Chem. Soc. 2007, 129, 5836.
[48]	Tong, X.; Beller, M.; Tse, M. K. J. Am. Chem. Soc. 2007, 129, 4906.
[49]	Liu, H.; Yu, J.; Wang, L.; Tong, X. Tetrahedron Lett. 2008, 49, 6924.
[50]	Tsujihara, T.; Takenaka, K.; Onitsuka, K.; Hatanaka, M.; Sasai, H. J. Am. Chem. Soc. 2009, 131, 3452. doi: 10.1021/ja809965e pmid: 19275254
[51]	Xu, T.; Wang, D.; Tong, X. Org. Lett. 2019, 21, 5368. doi: 10.1021/acs.orglett.9b02096 pmid: 31247755
[52]	Vinoth, P.; Vivekanand, T.; Suryavanshi, P. A.; Menéndez, J. C.; Sasai, H.; Sridharan, V. Org. Biomol. Chem. 2015, 13, 5175.
[53]	Liu, B.; Song, R.-J.; Ouyang, X.-H.; Li, Y.; Hu, M.; Li, J.-H. Chem. Commun. 2015, 51, 12819.
[54]	Chen, J.; Han, X.; Lu, X. Angew. Chem., Int. Ed. 2017, 56, 14698.
[55]	Malik, G.; Swyka, R. A.; Tiwari, V. K.; Fei, X.; Applegate, G. A.; Berkowitz, D. B. Chem. Sci. 2017, 8, 8050. doi: 10.1039/c7sc04083k pmid: 29568453