Research Progress on Transition Metal Catalyzed Hydrocarbonation Reactions of N-Allenamines

doi:10.6023/cjoc202406007

Abstract

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

Cite this article

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.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 37

Scheme 1. Regional conversion model of allenamides

Scheme 2. Hydrofunctionalization of allenamides

Scheme 3. Pd-catalyzed regiocontrollable hydroarylation reaction of allenamides

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

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

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

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

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

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

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

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

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

Scheme 13. Pd-catalyzed cyclization reaction of allenamides

Scheme 14. Ligand-controlled regiodivergent semireduction

Scheme 15. Palladium-catalyzed cycloisomerization of allenamides

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

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

Scheme 18. Gold-catalyzed intramolecular hydroarylation of allenamines

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

Scheme 20. Au-catalyzed aromatic hydrogenation of allenamine derivatives

Scheme 21. Au-catalyzed hydroarylation of allenamides with naphthol

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

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

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

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

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

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

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

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

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

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

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

Scheme 33. Copper-catalyzed hydroarylation of allenamides

Scheme 34. Ni-catalyzed hydroarylation of allenamides

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

Scheme 36. Intramolecular radical addition to allenamines

Scheme 37. Reaction of allenamines to construct 2-aminofuran

References 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.

过渡金属催化联烯胺类化合物的碳氢化反应研究进展