过渡金属催化联烯胺类化合物的碳氢化反应研究进展

doi:10.6023/cjoc202406007

摘要/Abstract

联烯胺作为一种富电子联烯类化合物, 由于其具有不同的反应位点和较高的反应活性, 近年来受到了广泛的关注. 联烯胺的双重反应性允许对氮原子的C(1)-C(3)位点进行区域和立体选择性的官能团化. 过渡金属催化联烯胺官能化, 选择性地获得近端或远端加合物, 在构建复杂的药物和天然产物骨架方面具有重要意义. 此文综述了近年来过渡金属催化联烯胺类化合物的碳氢化反应研究进展. 综述中的实例根据所使用的过渡金属类型进行分类, 此外, 还简要讨论了反应机理, 对于碳氢化反应的选择性调控和开发新反应类型至关重要.

关键词: 联烯胺, 碳氢化, 官能团化, 区域选择性

As an electron-rich diene compound, N-allenamines have received wide spread attention in recent years due to its different reaction sites and high reactivity. The dual reactivity of N-allenamines enables functionalization at C(1)-C(3) sites of the nitrogen atom, facilitating region- and stereoselective modifications. The transition metal-catalyzed functionalization of N-allenamines, which selectively yields either proximal or distal adducts, plays a crucial role in the synthesis of complex frameworks in drugs and natural products. The examples in the review are classified based on the type of transition metal used. In addition, this review briefly discusses the reaction mechanism, which is crucial for selective regulation of hydrocarbonnation reactions and the development of new reaction types.

Key words: N-allenamines, hydrocarbonation, functionalization, regioselectivity

引用此文

王君伟, 薛皓, 曲英瑜, 姜若楠, 闫法超, 刘会. 过渡金属催化联烯胺类化合物的碳氢化反应研究进展[J]. 有机化学, 2025, 45(1): 151-167.

Junwei Wang, Hao Xue, Yingyu Qu, Ruonan Jiang, Fachao Yan, Hui Liu. Research Progress on Transition Metal Catalyzed Hydrocarbonation Reactions of N-Allenamines[J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 151-167.

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

分享此文

图/表 37

图式1. 联烯胺的高区域性转化模型

Scheme 1. Regional conversion model of allenamides

图式2. 联烯胺化合物的碳氢化反应

Scheme 2. Hydrofunctionalization of allenamides

图式3. 钯催化联烯胺区域选择性芳氢化反应

Scheme 3. Pd-catalyzed regiocontrollable hydroarylation reaction of allenamides

图式4. 钯催化联烯胺与苯硼酸区域选择性芳氢化反应

Scheme 4. Pd-catalyzed regiocontrollable hydroarylation reaction of allenamides and phenylboronic acid

图式5. 钯催化联烯胺Metallo-ene/Suzuki串联反应

Scheme 5. Pd-catalyzed cascade Metallo-ene/Suzuki coupling reaction of allenamides

图式6. 钯催化联烯胺Heck选择性环化

Scheme 6. Pd-catalyzed cyclization-heck reaction of allenamides

图式7. 联烯胺Metallo-ene/Sonogashira串联反应

Scheme 7. Cascade Metallo-ene/Sonogashira coupling reaction of allenamides

图式8. 氢烷基化合成1,3-和1,4-烯炔

Scheme 8. Hydroalkylation to 1,3- and 1,4-enynes

图式9. 钯催化联烯胺metallo-ene/metallo-carbene串联反应

Scheme 9. Pd-catalyzed cascade metallo-ene cyclization/metallo-carbene coupling of allenamides

图式10. 钯/铜协同催化联烯胺的对映选择性曼尼西偶联反应

Scheme 10. Pd/Cu-catalyzed enantioselective Mannichcoupling of allenamides

图式11. 钯催化β-酮酸与联烯胺的不对称氢化反应

Scheme 11. Pd-catalyzed asymmetric decarboxylative addition of β-keto acids to allenamides

图式12. 钯催化联烯胺构建吲哚和异喹啉酮

Scheme 12. Pd-catalyzed construction of indole and isoquinolinone from allenamides

图式13. 钯催化联烯胺的环化反应

Scheme 13. Pd-catalyzed cyclization reaction of allenamides

图式14. 配体控制的区域发散半还原反应

Scheme 14. Ligand-controlled regiodivergent semireduction

图式15. 钯催化联烯胺环化异构化反应

Scheme 15. Palladium-catalyzed cycloisomerization of allenamides

图式16. 钌催化联烯胺与醛类化合物的转移氢化

Scheme 16. Ruthenium-catalyzed transfer hydrogenative coupling of allenamides to aldehydes

图式17. 钌催化伯醇与联烯胺的区域选择性和非对映选择性加成反应

Scheme 17. Regio- and diastereoselective Ru-catalyzed addition of primary alcohols to allenamides

图式18. 金催化的联烯胺分子内芳氢化反应

Scheme 18. Gold-catalyzed intramolecular hydroarylation of allenamines

图式19. 金催化环状联烯胺衍生物的分子之间反应

Scheme 19. Gold-catalyzed intermolecular reactions of cyclic allenamine derivatives

图式20. 金催化联烯胺衍生物的芳氢化反应

Scheme 20. Au-catalyzed aromatic hydrogenation of allenamine derivatives

图式21. Au催化萘酚与联烯胺的芳氢化反应

Scheme 21. Au-catalyzed hydroarylation of allenamides with naphthol

图式22. Au(I)催化萘酚与联烯胺的去芳构化反应

Scheme 22. Au(I)-catalyzed dearomatization of naphthols with allenamides

图式23. 金催化联烯胺合成苯并氮平类化合物

Scheme 23. Synthesis of benzazepines by gold-catalysed reactions of allenamides

图式24. Au(I)-催化Imino-Nazarov环化反应

Scheme 24. Au(I)-catalyzed Imino-Nazarov cyclization

图式25. 金催化醇、α-芳基-α-重氮酯和联烯胺

Scheme 25. Au(I)-catalyzed three-component reaction between alcohols, α-aryl-α-diazoesters and allenamides

图式26. 铜催化联烯胺和酮的还原偶联反应

Scheme 26. Cu-catalyzed reductive coupling of allenes and ketones

图式27. 铜催化联烯胺和酮的还原偶联反应

Scheme 27. Cu-catalyzed reductive coupling of allenes and ketones

图式28. 铜催化联烯胺和亚胺的还原偶联反应

Scheme 28. Cu-catalyzed reductive coupling of imines and allenamides

图式29. 铜催化联烯胺和酮的不对称还原偶联反应

Scheme 29. Asymmetric Cu-catalyzed reductive coupling of ketones and allenamides

图式30. 铜催化联烯胺和醛的还原偶联反应

Scheme 30. Cu-catalyzed reductive coupling of aldehydes and allenamides

图式31. 铜催化醛和联烯胺的反马氏加成反应

Scheme 31. Copper-catalyzed anti-Markovnikov addition of aldehydes to allenamides

图式32. 铜催化联烯胺和1,3-二羰基化合物碳氢化反应

Scheme 32. Cu-catalyzed hydrocarbonation of 1,3-dicarbonyl compounds with allenamides

图式33. 铜催化联烯胺的芳氢化反应

Scheme 33. Copper-catalyzed hydroarylation of allenamides

图式34. 镍催化联烯胺的芳氢化反应

Scheme 34. Ni-catalyzed hydroarylation of allenamides

图式35. 镍促进联烯胺和二氧化碳的羧基化反应

Scheme 35. Nickel-mediated carboxylation of carbamate-derived terminal allenamide

图式36. 联烯胺进行分子内自由基加成的反应

Scheme 36. Intramolecular radical addition to allenamines

图式37. 联烯胺构建2-氨基呋喃的反应

Scheme 37. Reaction of allenamines to construct 2-aminofuran

参考文献 89

[1]	Burton, B. S.; Pechman, H. V. Chem. Ber. 1887, 20, 145.
[2]	Ma, S. Chem. Rev. 2005, 105, 2829.
[3]	Ma, S. Acc. Chem. Res. 2009, 42, 1679.
[4]	Zimmer, R.; Dinesh, C. U.; Nandanan, E.; Khan, F. A. Chem. Rev. 2000, 100, 3067.
[5]	Nájera, C.; Beletskaya, I. P.; Yus, M. Chem. Soc. Rev. 2019, 48, 4515.
[6]	Zhan, G.; Du, W.; Chen, Y.-C. Chem. Soc. Rev. 2017, 46, 1675.
[7]	Hubert, A.; Viehe, H. J. Chem. Soc. C 1968, 228.
[8]	Wei, L-L.; Xiong, H.; Hsung, R. P. Acc. Chem. Res. 2003, 36, 773.
[9]	Hourtoule, M.; Miesch, L. Org. Biomol. Chem. 2022, 20, 9069.
[10]	Zhang, J.; Liang, W.; Yang, Y.; Yan, F.; Liu, H. Chin. J. Org. Chem. 2024, 44, 335 (in Chinese).
	(张剑, 梁万洁, 杨艺, 闫法超, 刘会, 有机化学, 2024, 44, 335.)
[11]	Blieck, R.; Taillefer, M.; Monnier, F. Chem. Rev. 2020, 120, 13545.
[12]	De Renzi, A.; Panunzi, A.; Saporito, A.; Vitagliano, A. J. Chem. Soc., Perkin Trans. 2 1983, 993.
[13]	Cui, J.; Meng, L.; Chi, X.; Liu, Q.; Zhao, P.; Zhang, D.; Chen, L.; Li, X.; Dong, Y.; Liu, H. Chem. Commun. 2019, 55, 4355.
[14]	(a) Dong, X.; Xu, L.-P.; Yang, Y.; Liu, Y.; Li, X.; Liu, Q.; Zheng, L.; Wang, F.; Liu, H. Org. Chem. Front. 2021, 8, 6009.
	(b) Sun, X.; Dong, X.; Liu, H.; Liu, Y. Adv. Synth. Catal. 2021, 363, 1527.
	(c) Dong, X.; Hou, Y.; Meng, F.; Liu, H-B.; Liu, H. Chin. J. Org. Chem. 2017, 37, 1088 (in Chinese).
	(董旭, 侯永正, 孟凡威, 刘洪波, 刘会, 有机化学, 2017, 37, 1088.)
	(d) Liu, Q.; Dong, X.; Li, J.; Xiao, J.; Dong, Y.; Liu, H. ACS Catal. 2015, 5, 6111.
[15]	Du, X.; Zhao, H.; Li, X.; Zhang, L.; Dong, Y.; Wang, P.; Zhang, D.; Liu, Q.; Liu, H. J. Org. Chem. 2021, 86, 13276.
[16]	Liang, H.; Yan, F.; Dong, X.; Liu, Q.; Wei, X.; Liu, S.; Dong, Y.; Liu, H. Chem. Commun. 2017, 53, 3138.
[17]	Yan, F.; Liang, H.; Song, J.; Cui, J.; Liu, Q.; Liu, S.; Wang, P.; Dong, Y.; Liu, H. Org. Lett. 2017, 19, 86.
[18]	Yan, F.; Liang, H.; Ai, B.; Liang, W.; Jiao, L.; Yao, S.; Zhao, P.; Liu, Q.; Dong, Y.; Liu, H. Org. Biomol. Chem. 2019, 17, 2651.
[19]	Li, J.; Meng, L.; Du, X.; Liu, Q.; Xu, L.; Zhang, L.; Sun, F.; Li, X.; Zhang, D.; Xiao, X. Org. Chem. Front. 2020, 7, 3880.
[20]	Inamoto, K.; Yamamoto, A.; Ohsawa, K.; Hiroya, K.; Sakamoto, T. Chem. Pharm. Bull. 2005, 53, 1502.
[21]	Husinec, S.; Petkovic, M.; Savic, V.; Simic, M. Synthesis 2012, 44, 399.
[22]	Blieck, R.; Taillefer, M.; Monnier, F. J. Org. Chem. 2019, 84, 11247.
[23]	Pradhan, T. R.; Lee, H. E.; Gonzalez‐Montiel, G. A.; Cheong, P. H. Y.; Park, J. K. Chem.-Eur. J. 2020, 26, 13826.
[24]	Liang, H.; Meng, L.; Chi, X.; Yao, S.; Chen, H.; Jiao, L.; Liu, Q.; Zhang, D.; Liu, H.; Dong, Y. Asian J. Org. Chem. 2018, 7, 1793.
[25]	Pradhan, T. R.; Kim, H. W.; Park, J. K. Angew. Chem., Int. Ed. 2018, 57, 9930.
[26]	Cao, C.; Yang, Y.; Li, X.; Liu, Y.; Liu, H.; Zhao, Z.; Chen, L. Eur. J. Org. Chem. 2021, 2021, 1538.
[27]	Chai, W.; Guo, B.; Zhang, Q.; Zi, W. Chem. Catal. 2022, 2, 1428.
[28]	Jang, D.-J.; Lee, S.; Lee, J.; Moon, D.; Ho Rhee, Y. Angew. Chem., Int. Ed. 2021, 60, 22166.
[29]	Zhu, X.; Li, R.; Yao, H.; Lin, A. Org. Lett. 2021, 23, 4630.
[30]	Hé douin, J.; Schneider, C.; Gillaizeau, I.; Hoarau, C. Org. Lett. 2018, 20, 6027.
[31]	Wang, D.-C.; Yang, T.-T.; Qu, G.-R.; Guo, H.-M. J. Org. Chem. 2022, 87, 14284.
[32]	Wang, J.; Li, L.; Chai, M.; Ding, S.; Li, J.; Shang, Y.; Zhao, H.; Li, D.; Zhu, Q. ACS Catal. 2021, 11, 12367.
[33]	Wang, D.-C.; Cheng, P.-P.; Yang, T.-T.; Wu, P.-P.; Qu, G.-R.; Guo, H.-M. Org. Lett. 2021, 23, 7865.
[34]	(a) Shen, Q.-W.; Wen, W.; Guo, Q.-X. Org. Lett. 2023, 25, 3163.
	(b) Guo, S.; Chen, J.; Yi, M.; Dong, L.; Lin, A.; Yao, H. Org. Chem. Front. 2021, 8, 1783.
[35]	Xue, Q.; Pu, Y.; Zhao, H.; Xie, X.; Zhang, H.; Wang, J.; Yan, L.; Shang, Y. Chem. Commun. 2024, 60, 3794.
[36]	Hajiloo Shayegan, M.; Li, Z.-Y.; Cui, X. Chem.-Eur. J. 2022, 28, e202103402.
[37]	Chen, C.; Tian, Z.; Liang, W.; Guo, J.; Xiao, P.; Wang, Z.; Zhang, L.; Liu, Q.; Liu, H. Asian J. Org. Chem. 2023, 12, e202300468.
[38]	Skucas, E.; Zbieg, J. R.; Krische, M. J. J. Am. Chem. Soc. 2009, 131, 5054
[39]	For ruthenium-catalyzed transfer hydrogenative coupling of alcohols to dienes, see: (a) Shibahara, F.; Bower, J. F.; Krische, M. J. Am. Chem. Soc. 2008, 130, 6338.
	(b) Shibahara, F.; Bower, J. F.; Krische, M. J. J. Am. Chem. Soc. 2008, 130, 14120.
	(c) Smejkal, T.; Han, H.; Breit, B.; Krische, M. J. J. Am. Chem. Soc. 2009, 131, 10366.
[40]	For ruthenium-catalyzed transfer hydrogenative coupling of alcohols to enynes, see: Patman, R. L.; Williams, V. M.; Bower, J. F.; Krische, M. J. Angew. Chem., Int. Ed. 2008, 47, 5220.
[41]	For ruthenium-catalyzed transfer hydrogenative coupling of alcohols to alkynes, see: (a) Patman, R. L.; Chaulagain, M. R.; Williams, V. M.; Krische, M. J. J. Am. Chem. Soc. 2009, 131, 2066.
	(b) Williams, V. M.; Leung, J. C.; Patman, R. L.; Krische, M. J. Tetrahedron 2009, 65, 5024.
[42]	For ruthenium-catalyzed transfer hydrogenative coupling of aldehydes to allenes, see: (a) Ngai, M.-Y.; Skucas, E.; Krische, M. J. Org. Lett. 2008, 10, 2705.
	(b) Grant, C. D.; Krische, M. J. Org. Lett. 2009, 11, 4485.
[43]	Zbieg, J. R.; McInturff, E. L.; Krische, M. J. Org. Lett. 2010, 12, 2514.
[44]	Watanabe, T.; Oishi, S.; Fujii, N.; Ohno, H. Org. Lett. 2007, 9, 4821.
[45]	Kimber, M. C. Org. Lett. 2010, 12, 1128.
[46]	Fernández-Casado, J.; Nelson, R.; Mascareñas, J. L.; López, F. Chem. Commun. 2016, 52, 2909.
[47]	Singh, S.; Elsegood, M. R. J.; Kimber, M. C. Synlett 2012, 2012, 565.
[48]	An, J.; Lombardi, L.; Grilli, S.; Bandini, M. Org. Lett. 2018, 20, 7380.
[49]	Ocello, R.; De Nisi, A.; Jia, M.; Yang, Q.; Monari, M.; Giacinto, P.; Bottoni, A.; Miscione, G. P.; Bandini, M. Chem.-Eur. J. 2015, 21, 18445.
[50]	(a) Yu, Y.; Zhang, Z.; Voituriez, A.; Rabasso, N.; Frison, G.; Marinetti, A.; Guinchard, X. Chem. Commun. 2021, 57, 10779.
	(b) Nicholls, L. D. M.; Wennemers, H. Chem.-Eur. J. 2021, 27, 17559.
[51]	Jia, M.; Cera, G.; Perrotta, D.; Monari, M.; Bandini, M. Chem.-Eur. J. 2014, 20, 9875.
[52]	Rocchigiani, L.; Jia, M.; Bandini, M.; Macchioni, A. ACS Catal. 2015, 5, 3911.
[53]	Hu, J.; Pan, S.; Zhu, S.; Yu, P.; Xu, R.; Zhong, G.; Zeng, X. J. Org. Chem. 2020, 85, 7896.
[54]	González‐Gómez, Á.; Domínguez, G.; Pérez‐Castells, J. Eur. J. Org. Chem. 2009, 2009, 5057.
[55]	Ma, Z.; He, S.; Song, W.; Hsung, R. P. Org. Lett. 2012, 14, 5736.
[56]	Liu, G.; Yu, S.; Hu, W.; Qiu, H. Chem. Commun. 2019, 55, 12675.
[57]	Banerjee, S.; Senthilkumar, B.; Patil, N. T. Org. Lett. 2019, 21, 180.
[58]	Hill, A. W.; Elsegood, M. R. J.; Kimber, M. C. J. Org. Chem. 2010, 75, 5406.
[59]	Klake, R. K.; Gargaro, S. L.; Gentry, S. L.; Elele, S. O.; Sieber, J. D. Org. Lett. 2019, 21, 7992.
[60]	Ho, D.B.; Gargaro, S.; Klake, R. K.; Sieber, J. D. J. Org. Chem. 2022, 87, 2142.
[61]	Collinsa, S.; Sieber, J. D. Chem. Commun. 2023, 59, 10087.
[62]	Gargaro, S. L.; Klake, R. K.; Burns, K. L.; Elele, S. O.; Gentry, S. L.; Sieber, J. D. Org. Lett. 2019, 21, 9753.
[63]	Agrawal, T.; Martin, R. T.; Collins, S.; Wilhelm, Z.; Edwards, M. D.; Gutierrez, O.; Sieber, J. D. J. Org. Chem. 2021, 86, 5026.
[64]	Collins, S.; Sieber, J. D. Org. Lett. 2023, 25, 1425.
[65]	Klake, R. K.; Sieber, J. D. Org. Lett. 2023, 25, 4730.
[66]	Blieck, R.; Lemouzy, S.; van der Lee, A.; Taillefer, M.; Monnier, F. Org. Lett. 2021, 23, 9199.
[67]	Blieck, R.; Abed Ali Abdine, R.; Taillefer, M.; Monnier, F. Org. Lett. 2018, 20, 2232.
[68]	Abed Ali Abdine, R.; Pagès, L.; Taillefer, M.; Monnier, F. Eur. J. Org. Chem. 2020, 48, 7466.
[69]	Liu, Y.; De Nisi, A.; Cerveri, A.; Monari, M.; Bandini, M. Org. Lett. 2017, 19, 5034.
[70]	Liu, Y.; Cerveri, A.; De Nisi, A.; Monari, M.; Nieto Faza, O.; Lopez, C. S.; Bandini, M. Org. Chem. Front. 2018, 5, 3231.
[71]	Saito, N.; Sugimura, Y.; Sato, Y. Synlett 2014, 25, 736.
[72]	Du, M.; Sun, Y.; Zhao, J.; Hu, H.; Sun, L.; Li, Y. Chin. Chem. Lett. 2023, 34, 108269.
[73]	Gui, Y.-Y.; Chen, X.-W.; Mo, X.-Y.; Yue, J.-P.; Yuan, R.; Liu, Y.; Liao, L.-L.; Ye, J.-H.; Yu, D.-G. J. Am. Chem. Soc. 2024, 146, 2919.
[74]	Wang, Y. Sci. Focus 2023, 18, 1 (in Chinese).
	(王野, 科学观察, 2023, 18, 1.)
[75]	Cui, J.; Song, J.; Liu, Q.; Liu, H.; Dong, Y. Chem. Asian J. 2018, 13, 482.
[76]	Song, J.; Liu, Q.; Liu, H.; Jiang, X. Eur. J. Org. Chem. 2018, 6, 696.
[77]	Shen, L.; Hsung, R. P. Org. Lett. 2005, 7, 775.
[78]	Mukherjee, R.; Basak, A. Synlett 2012, 23, 877.
[79]	Lu, N.; Zhang, Z.; Ma, N. Org. Lett. 2018, 20, 4318.
[80]	Yuan, X.; Tan, X.; Ding, N.; Liu, Y.; Li, X.; Zhao, Z. Org. Chem. Front. 2020, 7, 2725.
[81]	Koleoso, O. K.; Turner, M.; Plasser, F.; Kimber, M. C. Beilstein J. Org. Chem. 2020, 16, 1983.
[82]	Koike, T.; Akita, M. Org. Chem. Front. 2016, 3, 1345.
[83]	Courant, T.; Masson, G. Chem.-Eur. J. 2012, 18, 423.
[84]	Quintavalla, A.; Veronesi, R.; Speziali, L.; Martinelli, A.; Zaccheroni, N.; Mummolo, L.; Lombardo, M. Adv. Synth. Catal. 2022, 364, 362.
[85]	Wan, Y.; Zhang, J.; Chen, Y.; Kong, L.; Luo, F.; Zhu, G. Org. Biomol. Chem. 2017, 15, 7204.
[86]	Kondoh, A.; Ishikawa, S.; Aoki, T.; Terada, M. Chem. Commun. 2016, 52, 12513.
[87]	Zhang, J.; Wu, M.; Lu, W.; Wang, S.; Zhang, Y.; Cheng, C.; Zhu, G. J. Org. Chem. 2017, 82, 11134.
[88]	Brasholz, M.; Reissig, H.-U.; Zimmer, R. Acc. Chem. Res. 2009, 42, 45.
[89]	Alonso, J. M.; Almendros, P. Chem. Rev. 2021, 121, 4193.