经历金属氢物种制备手性叔胺的不对称催化研究进展

doi:10.6023/cjoc202206032

摘要/Abstract

手性叔胺作为一种重要的化合物骨架, 存在于各种药物、天然产物和有机功能材料中, 因而受到合成化学家们的重视. 目前已有几种不同的经历金属氢物种的合成手性叔胺的方法被报道. 根据不同的反应类型, 本文从不对称氢胺化、不对称氢化、不对称还原胺化和“借氢”策略中醇的不对称胺化四个方面对近年来的研究进展进行总结. 同时介绍了各策略中相应反应的机理, 并对该领域的未来发展做了展望.

关键词: 手性叔胺, 不对称催化, 金属氢物种, 氢化, 氢胺化

Chiral tertiary amines, as a class of important skeleton, exist in various drugs, natural products, and organic functional materials. Therefore, the development of efficient synthetic methods for the preparation of chiral tertiary amines has attracted much attention from chemists and become one of the research hotspots in recent years. Until now, several asymmetric catalytic methods involving metal-hydride species have been developed. According to different reaction types, the research progress in recent years is summarized from four aspects: asymmetric hydroamination, asymmetric hydrogenation, asymmetric reductive amination, and asymmetric amination of alcohols via the ‘borrowing hydrogen’ strategy. At the same time, the corresponding reaction mechanism of each strategy is introduced, and the future development of this field is envisioned.

Key words: tertiary amine, asymmetric catalysis, metal-hydride species, hydrogenation, hydroamination

引用此文

范天翔, 刘媛媛. 经历金属氢物种制备手性叔胺的不对称催化研究进展[J]. 有机化学, 2022, 42(10): 3280-3294.

Tianxiang Fan, Yuanyuan Liu. Recent Advances in Synthesis of Chiral Tertiary Amines via Asymmetric Catalysis Involving Metal-Hydride Species[J]. Chinese Journal of Organic Chemistry, 2022, 42(10): 3280-3294.

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

分享此文

图/表 41

图1. 手性胺药物

Figure 1. Chiral amine drugs

图式1. 不对称催化合成手性胺方法

Scheme 1. Asymmetric catalytic synthesis of chiral amines

图式2. 铜催化的烯烃不对称氢胺化反应

Scheme 2. Copper-catalyzed asymmetric hydroamination of olefins

图式3. 铜催化的乙烯基硅烷类底物不对称氢胺化

Scheme 3. Copper-catalyzed asymmetric hydroamination of vinylsilanes

图式4. 铜催化未活化内烯烃的不对称氢胺化

Scheme 4. Copper-catalyzed asymmetric hydroamination of unactivated internal alkenes

图式5. 导向基导向的铜催化二取代烯烃的不对称氢胺化

Scheme 5. Directing group-directed copper-catalyzed asymmetric hydroamination of disubstituted olefins

图式6. 硼、膦官能团化烯烃的不对称氢胺化

Scheme 6. Asymmetric hydroamination of boron- and phosphine-functionalized olefins

图式7. 铜催化的1-三氟甲基烯烃不对称氢胺化

Scheme 7. Copper-catalyzed asymmetric hydroamination of 1- trifluoromethylalkenes

图式8. 不对称氢胺化合成二胺

Scheme 8. Synthesis of 1,2-diamine by asymmetric hydroamination

图式9. 不对称氢胺化合成γ-氨基醇

Scheme 9. Synthesis of γ-amino alcohols by asymmetric hydroamination

图式10. 铜催化的张力三取代烯的不对称氢胺化反应

Scheme 10. Copper-catalyzed hydroamination of strained trisubstituted alkenes

图式11. 铜催化的2H-苯并吡喃不对称氢胺化反应

Scheme 11. Copper-catalyzed asymmetric hydroamination of 2H-benzopyranes

图式12. 铑催化烯胺不对称氢胺化合成1,2-二胺

Scheme 12. Rhodium-catalyzed asymmetric hydroamination of allyl imines to 1,2-diamines

图式13. 铑催化的炔烃及联烯的不对称氢胺化反应

Scheme 13. Rhodium-catalyzed asymmetric hydroamination of alkynes and allenes

图式14. 铑催化的不对称氢胺化反应机理

Scheme 14. Mechanism of rhodium-catalyzed asymmetric hydroamination

图式15. 铑催化内炔和联烯的分子内不对称氢胺化反应

Scheme 15. Rhodium-catalyzed intramolecular hydroamination of internal alkynes and allenes

图式16. 铑催化的共轭二烯的不对称氢胺化反应

Scheme 16. Rhodium-catalyzed asymmetric hydroamination of conjugated dienes

图式17. 钯催化的1,3-共轭二烯不对称氢胺化反应

Scheme 17. Palladium-catalyzed asymmetric hydroamination of 1,3-conjugated dienes

图式18. 钯催化共轭二烯的不对称氢胺化机理

Scheme 18. Mechanism of palladium-catalyzed asymmetric hydroamination of conjugated diene

图式19. 钯钯催化双取代内共轭二烯的不对称氢胺化

Scheme 19. Palladium-catalyzed asymmetric hydroamination of disubstituted internal conjugated dienes

图式20. 钯催化内共轭二烯的不对称氢胺化机理

Scheme 20. Mechanism of asymmetric hydroamination of internal conjugated diene catalyzed by palladium

图式21. 钯催化二烯与吡唑的不对称氢胺化反应

Scheme 21. Palladium-catalyzed asymmetric hydroamination of dienes with pyrazoles

图式22. 镍催化支链二烯与仲胺的不对称氢胺化反应

Scheme 22. Nickel-catalyzed asymmetric hydroamination of secondary amine with branched dienes

图式23. 镍催化二烯与仲胺的不对称氢胺化反应机理

Scheme 23. Mechanism of asymmetric hydroamination of diene with secondary amine catalyzed by nickel

图式24. 镍催化直链二烯与仲胺的不对称氢胺化反应

Scheme 24. Nickel-catalyzed asymmetric hydroamination of linear dienes with secondary amine

图式25. 钛催化不对称氢化烯胺合成手性叔胺

Scheme 25. Ti-catalyzed synthesis of chiral tertiary amine by asymmetric hydrogenation

图式26. 钌催化不对称氢化烯胺合成手性叔胺

Scheme 26. Synthesis of chiral tertiary amine by ruthenium- catalyzed asymmetric hydrogenation

图式27. 铑催化不对称氢化未官能团化烯胺

Scheme 27. Rhodium-catalyzed asymmetric hydrogenation of unfunctionalized enamines

图式28. 铑催化不对称氢化环内烯胺

Scheme 28. Rhodium-catalyzed asymmetric hydrogenation of endo-cyclic enamines

图式29. 铑催化不对称氢化环外烯胺

Scheme 29. Rhodium-catalyzed asymmetric hydrogenation of exo-cyclic enamines

图式30. 铑催化不对称氢化环外烯胺机理

Scheme 30. Mechanism of rhodium-catalyzed asymmetric hydrogenation of exo-cyclic enamines

图式31. 铱催化不对称氢化烯胺

Scheme 31. Iridium-catalyzed asymmetric hydrogenation of enamine

图式32. 铱催化不对称氢化环状亚胺盐

Scheme 32. Iridium-catalyzed asymmetric hydrogenation of cyclic imine salts

图式33. 铱催化不对称还原胺化反应

Scheme 33. Iridium-catalyzed asymmetric reductive amination reaction

图式34. 铑催化不对称还原胺化反应

Scheme 34. Rhodium-catalyzed asymmetric reductive amination reaction

图式35. 钌催化不对称串联还原胺化反应

Scheme 35. Ruthenium-catalyzed asymmetric cascade reaction involving reductive amination

图式36. 钌催化的串联还原胺化反应

Scheme 36. Ruthenium-catalyzed cascade reaction involving reductive amination

图式37. 借氢策略反应机理

Scheme 37. Reaction mechanism of borrowing hydrogen strategy

图式38. 借氢策略合成手性哌啶

Scheme 38. Synthesis of chiral piperidine by borrowing hydrogen strategy

图式39. 借氢策略合成哌啶的机理

Scheme 39. Mechanism of piperidine synthesis by borrowing hydrogen strategy

图式40. 借氢策略合成哌啶生物碱

Scheme 40. Synthesis of piperidine alkaloids by borrowing hydrogen strategy

参考文献 53

[1]	(a) Onyeagusi, C. I.; Malcolmson, S. J. ACS Catal. 2020, 10, 12507. doi: 10.1021/acscatal.0c03569 pmid: 18095713
	(b) Robert-Paganin, J.; Pylypenko, O.; Kikuti, C.; Sweeney, H. L.; Houdusse, A. Chem. Rev. 2020, 120, 5. doi: 10.1021/acs.chemrev.9b00264 pmid: 18095713
	(c) Cai, M.; Xu, K.; Li, Y.; Nie, Z.; Zhang, L.; Luo, S. J. Am. Chem. Soc. 2021, 143, 1078. doi: 10.1021/jacs.0c11787 pmid: 18095713
	(d) Mukherjee, S.; Yang, J. W.; Hoffmann, S.; List, B. Chem. Rev. 2007, 107, 5471. pmid: 18095713
	(e) Hembury, G. A.; Borovkov, V. V.; Inoue, Y. Chem. Rev. 2008, 108, 1. pmid: 18095713
[2]	https://njardarson.lab.arizona.edu/content/top-pharmaceuticals-poster
[3]	(a) Roesky, P. W.; Müller, T. E. Angew. Chem., Int. Ed. 2003, 42, 2708. doi: 10.1002/anie.200301637
	(b) Müller, T. E.; Beller, M. Chem. Rev. 1998, 98, 675. doi: 10.1021/cr960433d
	(c) Müller, T. E.; Hultzsch, K. C.; Yus, M.; Foubelo, F.; Tada, M. Chem. Rev. 2008, 108, 3795. doi: 10.1021/cr0306788
[4]	(a) Zhang, Z.; Butt, N. A.; Zhang, W. Chem. Rev. 2016, 116, 14769. doi: 10.1021/acs.chemrev.6b00564
	(b) Barrios-Rivera, J.; Xu, Y.; Wills, M.; Vyas, V. K. Org. Chem. Front. 2020, 7, 3312. doi: 10.1039/D0QO00794C
	(c) Fleury, B., N.; Castillón, S.; Claver, C. ChemCatChem 2010, 2, 1346. doi: 10.1002/cctc.201000078
	(d) Xie, J.-H.; Zhu, S.-F.; Zhou, Q.-L. Chem. Rev. 2011, 111, 1713. doi: 10.1021/cr100218m
[5]	Reshi, N. U. D.; Saptal, V. B.; Beller, M.; Bera, J. K. ACS Catal. 2021, 11, 13809. doi: 10.1021/acscatal.1c04208
[6]	Gomez, S.; Peters, J. A.; Maschmeyer, T. Adv. Synth. Catal. 2002, 344, 1037.
[7]	Wu, Z.; Du, S.; Gao, G.; Yang, W.; Yang, X.; Huang, H.; Chang, M. Chem. Sci. 2019, 10, 4509. doi: 10.1039/C9SC00323A
[8]	(a) Swain, S. P.; Shri, O.; Ravichandiran, V. Mol. Catal. 2021, 508, 111576.
	(b) Tang, S.; Li, Z.; Shao, Y.; Sun, J. Org. Lett. 2019, 21, 7228. doi: 10.1021/acs.orglett.9b02435
[9]	Miki, Y.; Hirano, K.; Satoh, T.; Miura, M. Angew. Chem., Int. Ed. 2013, 52, 10830. doi: 10.1002/anie.201304365
[10]	Zhu, S.; Niljianskul, N.; Buchwald, S. L. J. Am. Chem. Soc. 2013, 135, 15746. doi: 10.1021/ja4092819
[11]	(a) Jordan, A. J.; Lalic, G.; Sadighi, J. P. Chem. Rev. 2016, 116, 8318. doi: 10.1021/acs.chemrev.6b00366 pmid: 18616323
	(b) Deutsch, C.; Krause, N. Chem. Rev. 2008, 108, 2916. doi: 10.1021/cr0684321 pmid: 18616323
[12]	Snieckus, V.; Green, J. Synlett 2014, 25, 2258. doi: 10.1055/s-0034-1379212
[13]	(a) Miki, Y.; Hirano, K.; Satoh, T.; Miura, M. Org. Lett. 2014, 16, 1498. doi: 10.1021/ol5003219
	(b) Perego, L. A.; Blieck, R.; Groué, A.; Monnier, F.; Taillefer, M.; Ciofini, I.; Grimaud, L. ACS Catal. 2017, 7, 4253. doi: 10.1021/acscatal.7b00911
[14]	Perego, L. A.; Blieck, R.; Michel, J.; Ciofini, I.; Grimaud, L.; Taillefer, M.; Monnier, F. Adv. Synth. Catal. 2017, 359, 4388. doi: 10.1002/adsc.201700965
[15]	Niljianskul, N.; Zhu, S.; Buchwald, S. L. Angew. Chem., Int. Ed. 2015, 54, 1638. doi: 10.1002/anie.201410326
[16]	Yang, Y.; Shi, S.-L.; Niu, D.; Liu, P.; Buchwald, S. L. Science 2015, 349, 62. doi: 10.1126/science.aab3753 pmid: 26138973
[17]	Xi, Y.; Butcher, T. W.; Zhang, J.; Hartwig, J. F. Angew. Chem., Int. Ed. 2016, 55, 776. doi: 10.1002/anie.201509235
[18]	Nishikawa, D.; Hirano, K.; Miura, M. J. Am. Chem. Soc. 2015, 137, 15620. doi: 10.1021/jacs.5b09773 pmid: 26653275
[19]	Takata, T.; Nishikawa, D.; Hirano, K.; Miura, M. Chem.-Eur. J. 2018, 24, 10975. doi: 10.1002/chem.201802491
[20]	Takata, T.; Hirano, K.; Miura, M. Org. Lett. 2019, 21, 4284. doi: 10.1021/acs.orglett.9b01471
[21]	Yu, L.; Somfai, P. Angew. Chem., Int. Ed. 2019, 58, 8551. doi: 10.1002/anie.201902642
[22]	Ichikawa, S.; Dai, X.-J.; Buchwald, S. L. Org. Lett. 2019, 21, 4370. doi: 10.1021/acs.orglett.9b01592 pmid: 31099584
[23]	Ichikawa, S.; Buchwald, S. L. Org. Lett. 2019, 21, 8736. doi: 10.1021/acs.orglett.9b03356 pmid: 31625750
[24]	Feng, S.; Hao, H.; Liu, P.; Buchwald, S. L. ACS Catal. 2020, 10, 282. doi: 10.1021/acscatal.9b04871
[25]	Yang, Q.; Li, S.; Wang, J. ChemCatChem 2020, 12, 3202. doi: 10.1002/cctc.202000601
[26]	Vanable, E. P.; Kennemur, J. L.; Joyce, L. A.; Ruck, R. T.; Schultz, D. M.; Hull, K. L. J. Am. Chem. Soc. 2019, 141, 739. doi: 10.1021/jacs.8b09811 pmid: 30614700
[27]	Berthold, D.; Breit, B. Org. Lett. 2018, 20, 598. doi: 10.1021/acs.orglett.7b03708 pmid: 29350041
[28]	Velasco-Rubio, Á.; Bernárdez, R.; Varela, J. A.; Saá, C. J. Org. Chem. 2021, 86, 10889. doi: 10.1021/acs.joc.1c01268
[29]	Yang, X.-H.; Dong, V. M. J. Am. Chem. Soc. 2017, 139, 1774. doi: 10.1021/jacs.6b12307
[30]	Adamson, N. J.; Hull, E.; Malcolmson, S. J. J. Am. Chem. Soc. 2017, 139, 7180. doi: 10.1021/jacs.7b03480 pmid: 28453290
[31]	Park, S.; Malcolmson, S. J. ACS Catal. 2018, 8, 8468. doi: 10.1021/acscatal.8b01914
[32]	Jiu, A. Y.; Slocumb, H. S.; Yeung, C. S.; Yang, X.-H.; Dong, V. M. Angew. Chem., Int. Ed. 2021, 60, 19660. doi: 10.1002/anie.202105679
[33]	(a) Zhang, Z.; Butt, N. A.; Zhou, M.; Liu, D.; Zhang, W. Chin. J. Chem. 2018, 36, 443. doi: 10.1002/cjoc.201800053 pmid: 32491839
	(b) Quan, M.; Wu, L.; Yang, G.; Zhang, W. Chem. Commun. 2018, 54, 10394. doi: 10.1039/C8CC04932G pmid: 32491839
	(c) Wu, L.; Yang, G.; Zhang, W. CCS Chem. 2020, 2, 623. doi: 10.31635/ccschem.019.201900064 pmid: 32491839
	(d) Clevenger, A. L.; Stolley, R. M.; Aderibigbe, J.; Louie, J., Chem. Rev. 2020, 120, 6124. doi: 10.1021/acs.chemrev.9b00682 pmid: 32491839
	(e) Shi, D.; Wojcieszak, R.; Paul, S.; Marceau, E. Catalysts 2019, 9, 451. doi: 10.3390/catal9050451 pmid: 32491839
	(f) Mukherjee, A.; Milstein, D. ACS Catal. 2018, 8, 11435. doi: 10.1021/acscatal.8b02869 pmid: 32491839
[34]	Pawlas, J.; Nakao, Y.; Kawatsura, M.; Hartwig, J. F. J. Am. Chem. Soc. 2002, 124, 3669. pmid: 11929257
[35]	Tran, G.; Shao, W.; Mazet, C. J. Am. Chem. Soc. 2019, 141, 14814. doi: 10.1021/jacs.9b07253
[36]	Long, J.; Wang, P.; Wang, W.; Li, Y.; Yin, G. iScience 2019, 22, 369. doi: 10.1016/j.isci.2019.11.008
[37]	Abdine, R. A. A.; Hedouin, G.; Colobert, F.; Wencel-Delord, J. ACS Catal. 2021, 11, 215. doi: 10.1021/acscatal.0c03353
[38]	Lee, N. E.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 5985. doi: 10.1021/ja00092a066
[39]	Tararov, V. I.; Kadyrov, R.; Riermeier, T. H.; Holz, J.; Börner, A. Tetrahedron Lett. 2000, 41, 2351. doi: 10.1016/S0040-4039(00)00197-0
[40]	Hou, G.-H.; Xie, J.-H.; Wang, L.-X.; Zhou, Q.-L. J. Am. Chem. Soc. 2006, 128, 11774. doi: 10.1021/ja0644778
[41]	Hou, G.-H.; Xie, J.-H.; Yan, P.-C.; Zhou, Q.-L. J. Am. Chem. Soc. 2009, 131, 1366. doi: 10.1021/ja808358r
[42]	Yan, P.-C.; Xie, J.-H.; Hou, G.-H.; Wang, L.-X.; Zhou, Q.-L. Adv. Synth. Catal. 2009, 351, 3243. doi: 10.1002/adsc.200900602
[43]	Yan, P.; Xie, J.; Zhou, Q. Chin. J. Chem. 2010, 28, 1736. doi: 10.1002/cjoc.201090293
[44]	Ji, Y.; Feng, G.-S.; Chen, M.-W.; Shi, L.; Du, H.; Zhou, Y.-G. Org. Chem. Front. 2017, 4, 1125. doi: 10.1039/C7QO00060J
[45]	(a) Yasukawa, T.; Masuda, R.; Kobayashi, S. Nat. Catal. 2019, 2, 1088. doi: 10.1038/s41929-019-0371-y
	(b) Huang, H.; Wu, Z.; Gao, G.; Zhou, L.; Chang, M. Org. Chem. Front. 2017, 4, 1976. doi: 10.1039/C7QO00400A
	(c) Huang, H.; Liu, X.; Zhou, L.; Chang, M.; Zhang, X. Angew. Chem., Int. Ed. 2016, 55, 5309. doi: 10.1002/anie.201601025
	(d) Chang, M.; Liu, S.; Huang, K.; Zhang, X. Org. Lett. 2013, 15, 4354. doi: 10.1021/ol401851c
	(e) Chi, Y.; Zhou, Y.-G.; Zhang, X. J. Org. Lett. 2003, 68, 4120.
[46]	Jagadeesh, R. V.; Murugesan, K.; Alshammari, A. S.; Neumann, H.; Pohl, M.-M.; Radnik, J.; Beller, M. Science 2017, 358, 326. doi: 10.1126/science.aan6245
[47]	Gilbert, S. H.; Tin, S.; Fuentes, J. A.; Fanjul, T.; Clarke, M. L. Tetrahedron 2021, 80, 131863.
[48]	Chen, Y.; He, Y.-M.; Zhang, S.; Miao, T.; Fan, Q.-H. Angew. Chem., Int. Ed. 2019, 58, 3809. doi: 10.1002/anie.201812647
[49]	Wang, L.-R.; Chang, D.; Feng, Y.; He, Y.-M.; Deng, G.-J.; Fan, Q.-H. Org. Lett. 2020, 22, 2251. doi: 10.1021/acs.orglett.0c00444
[50]	(a) Liu, Y.; Tao, R.; Lin, Z.-K.; Yang, G.; Zhao, Y. Nat. Commun. 2021, 12, 5035. doi: 10.1038/s41467-021-25268-1
	(b) Yang, G.; Pan, J.; Ke, Y.-M.; Liu, Y.; Zhao, Y. Angew. Chem., Int. Ed. 2021, 60, 20689. doi: 10.1002/anie.202106514
	(c) Xi, X.; Li, Y.; Wang, G.; Xu, G.; Shang, L.; Zhang, Y.; Xia, L. Org. Biomol. Chem. 2019, 17, 7651. doi: 10.1039/C9OB01417A
	(d) Corma, A.; Navas, J.; Sabater, M. J. Chem. Rev. 2018, 118, 1410. doi: 10.1021/acs.chemrev.7b00340
	(e) Irrgang, T.; Kempe, R. Chem. Rev. 2019, 119, 2524. doi: 10.1021/acs.chemrev.8b00306
[51]	(a) Zhang, Y.; Lim, C.-S.; Sim, D. S. B.; Pan, H.-J.; Zhao, Y. Angew. Chem., Int. Ed. 2014, 53, 1399. doi: 10.1002/anie.201307789
	(b) Lim, C. S.; Quach, T. T.; Zhao, Y. Angew. Chem., Int. Ed. 2017, 56, 7176. doi: 10.1002/anie.201703704
	(c) Yang, P.; Zhang, C.; Ma, Y.; Zhang, C.; Li, A.; Tang, B.; Zhou, J. S. Angew. Chem., Int. Ed. 2017, 56, 14702. doi: 10.1002/anie.201708949
	(d) Xu, G.; Yang, G.; Wang, Y.; Shao, P.-L.; Y.; Xia, L.; Zhao, Y. Angew. Chem., Int. Ed. 2019, 58, 14082. doi: 10.1002/anie.201906199
	(e) Pan, H.-J.; Lin, Y.; Gao, T.; Lau, K. K.; Feng, W.; Yang, B.; Zhao, Y. Angew. Chem., Int. Ed. 2021, 60, 18599. doi: 10.1002/anie.202101517
	(f) Rong, Z.-Q.; Yu, Z.; Weng, C.; Yang, L.-C.; Lu, S.; Lan, Y.; Zhao, Y. ACS Catal. 2020, 10, 9464. doi: 10.1021/acscatal.0c02468
[52]	Fujita, K.-i.; Fujii, T.; Yamaguchi, R. Org. Lett. 2004, 6, 3525. doi: 10.1021/ol048619j
[53]	Miao, L.; DiMaggio, S. C.; Shu, H.; Trudell, M. L. Org. Lett. 2009, 11, 1579. doi: 10.1021/ol9002288 pmid: 19320505