亚胺及其类似物的催化不对称炔基化反应新进展

doi:10.6023/cjoc202007043

摘要/Abstract

手性炔丙胺是天然产物和药物活性分子不对称全合成中常用的关键中间体, 亚胺及其类似物的不对称炔基化反应可以为该砌块提供高效高对映选择性的合成路径; 此外通过合理的底物和反应设计, 亚胺的不对称炔基化反应还能作为一系列串联反应的起点, 来合成多种结构新颖的含氮杂环化合物. 因此, 亚胺及其类似物的高效高对映选择性炔基化反应得到合成化学家们持续关注. 按照底物类型, 主要分为醛亚胺的不对称炔基化和酮亚胺的不对称炔基化两大部分, 介绍了亚胺及其类似物的不对称炔基化反应在过去十年中的研究进展. 对这些反应的机理、优势与不足之处以及该反应在合成中的应用进行简要讨论, 从而为拓展该反应在合成中的应用提供一些有益参考和借鉴.

关键词: 手性炔丙胺, 不对称炔基化, 醛亚胺, 酮亚胺, 含氮杂环化合物

Chiral propargyl amines are key intermediates in the asymmetric total synthesis of natural products and bioactive compounds. The asymmetric alkynylation of imine and its analogues can provide a highly efficient and enantioselective synthetic route for these chiral building blocks. In addition, through rational substrate and reaction design, the asymmetric alkynylation of imines can be used as the starting point of a series of cascade reactions to synthesize a variety of novel nitrogen-heterocyclic compounds. Therefore, highly efficient and enantioselective alkynylation of imines and their analogues has attracted the continuous attention of synthetic chemists. According to the types of substrate, the research progress in asymmetric alkynylation of imines and their analogues over the past decade is introduced, which is divided into two parts: asymmetric alkynylation of aldimines and asymmetric alkynylation of ketoimines. The reaction mechanism and their advantages and disadvantages, together their synthetic applications will be briefly introduced, hoping to provide some useful inspiration for expanding the application of this reaction in synthesis.

Key words: chiral propargyl amine, asymmetric alkynylation, aldimine, ketoimine, nitrogen-heterocyclic compound

引用此文

周淑蕊, 温凯歌, 曾兴平. 亚胺及其类似物的催化不对称炔基化反应新进展[J]. 有机化学, 2021, 41(2): 471-489.

Shurui Zhou, Kaige Wen, Xingping Zeng. Recent Progress in Catalytic Asymmetric Alkynylation of Imines[J]. Chinese Journal of Organic Chemistry, 2021, 41(2): 471-489.

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

分享此文

图/表 43

图式1. 亚胺的不对称炔基化反应

Scheme 1. Asymmetric alkylation of imines

图式2. 氨基醇类三齿配体参与催化的不对称炔基化反应

Scheme 2. Tridentate ligand catalyzed asymmetric alkynylation

图式3. 3,3'-二溴联萘酚配体参与催化的不对称炔基化反应

Scheme 3. Enantioselective alkylation catalyzed by 3,3'-di- bromo-BINOL complex

图式4. N-磺酰基醛亚胺的不对称炔基化反应

Scheme 4. Enantioselective alkylation of N-sulfonyl aldimines

图式5. 原位生成亚胺的不对称炔基化反应

Scheme 5. Enantioselective alkynylation of in situ generated aldimines

图式6. N-芳基甘氨酸酯与末端炔的不对称脱氢偶联反应

Scheme 6. Enantioselective cross-dehydrogenative coupling of N-aryl glycine esters with terminal alkynes

图式7. 基于不对称炔基化衍生的串联反应合成

Scheme 7. Asymmetric alkynylation derived cascade reactions

图式8. 环状偶氮甲碱亚胺的不对称加成反应

Scheme 8. Asymmetric alkynylation of C,N-cyclic azomethine imines

图式9. 铜催化喹啉衍生物的不对称炔基化反应

Scheme 9. Asymmetric copper-catalyzed quinoline alkynylation

图式10. 异喹啉的不对称去芳构化炔基化反应

Scheme 10. Asymmetric dearomative alkynylation of isoquinolines

图式11. 七元环状亚胺的不对称炔基化反应

Scheme 11. Asymmetric alkynylation of 7-membered cyclic imine

图式12. 苯并六元环状磺酰亚胺的不对称炔基化反应

Scheme 12. Asymmetric alkynylation of benzo[e][1,2,3]-oxa- thiazine 2,2-dioxides

图式13. 脯氨醇作为配体催化的不对称炔基化反应

Scheme 13. Diarylprolinol as a ligand for enantioselective alkynylation

图式14. 高速球磨条件下的不对称炔基化反应

Scheme 14. Asymmetric alkynylation in a ball mill

图式15. N-酰基四氢异喹啉衍生物与末端炔的交叉脱氢偶联反应

Scheme 15. Enantioselective catalytic cross-dehydrogenative coupling (CDC) of N-carbamoyl tetrahydroisoquinolines and terminal alkynes

图式16. 基于四氢异喹啉的N-酰基半缩醛胺的不对称炔基化反应

Scheme 16. Enantioselective alkynylation of tetrahydroisoquinoline based N-acyl hemiaminals

图式17. 协同催化的四氢异喹啉与末端炔的交叉脱氢偶联反应

Scheme 17. Synergistic photocatalytic and copper-catalyzed CDC reaction between tertiary amines and terminal alkynes

图式18. 双金属协同催化的交叉脱氢偶联反应

Scheme 18. Bimetallic cooperatively catalyzed cross-dehydro- genative coupling (CDC) reaction

图式19. 串联不对称炔基化/内酰胺化合成异吲哚啉酮衍生物

Scheme 19. Cascade asymmetric alkynylation/lactamization to enantiomerically enriched isoindolinones

图式20. 基于不对称A3反应的串联反应

Scheme 20. Cascade reactions based on asymmetric A3 reaction

图式21. 高速球磨条件下的不对称A3反应

Scheme 21. Asymmetric A3 reaction under ball-milling conditions

图式22. 串联不对称A3/环羧基化合成噁唑烷酮衍生物

Scheme 22. Tandem asymmetric A3 coupling-carboxylative cyclization sequence to 2-oxazolidinones

图式23. 手性双咪唑啉三齿配体参与催化的A3反应

Scheme 23. Chiral bis(imidazoline)-Cu(I) catalyzed A3 reaction

图式24. 手性双咪唑啉-Cu(I)络合物催化的在水相中的A3反应

Scheme 24. Chiral bis(imidazoline)-Cu(I) complex catalyzed A3 reaction in water

图式25. 从末端炔出发制备手性联烯

Scheme 25. Synthesis of chiral allenes from terminal alkynes

图式26. (R,R)-N-PINAP-Cu(I)络合物催化的不对称A3反应

Scheme 26. (R,R)-N-PINAP-Cu(I) complex catalyzed A3 reaction

图式27. 从末端炔出发制备N-烯丙基吡咯衍生物

Scheme 27. Synthesis of chiral N-allyl pyrrole from alkynes

图式28. 四氢异喹啉参与的不对称A3反应及其应用

Scheme 28. Tetrahydroisoquinoline based asymmetric A3 reaction and its application

图式29. 13-甲基四氢原小檗碱类生物碱的对映选择性全合成

Scheme 29. Asymmetric total syntheses of 13-methyltetrahy- droprotoberberine alkaloids

图式30. 手性StackPhos配体-铜络合物催化的不对称A3反应

Scheme 30. Chiral stackPhos-Cu(I) complex catalyzed enantioselective A3 reaction and its application

图式31. 手性StackPhim配体-铜络合物催化的不对称A3反应

Scheme 31. Chiral stackPhim-Cu(I) complex catalyzed asymmetric A3 reaction

图式32. 手性Br?nsted酸-铜协同催化的不对称A3反应

Scheme 32. Asymmetric A3 reaction enabled by synergistic Br?nsted acids and Cu(I) catalysis

图式33. 首例α-三氟甲基亚胺酯的高对映选择性炔基化反应

Scheme 33. First highly enantioselective alkynylation of α- ketoimine ester

图式34. Zn-BINOL催化的的高对映选择性炔基化反应

Scheme 34. Zn-BINOL catalyzed highly enantioselective alkynylations

图式35. Phebox-Rh催化α-酮酸酯亚胺的高对映选择性炔基化反应

Scheme 35. Phebox-Rh catalyzed highly enantioselective alkynylation of α-ketoimine ester

图式36. 炔基-Rh(III)络合物催化的高对映选择性炔基化反应

Scheme 36. (Alkynyl)rhodium(III) complexes catalyzed highly enantioselective alkynylation

图式37. 非环状简单酮亚胺的不对称炔基化反应

Scheme 37. Catalytic asymmetric alkynylation of acyclic ketoimines derived from simple ketones

图式38. 药物分子KAE069的不对称全合成

Scheme 38. Total synthesis of drug molecule KAE069

图式39. 靛红亚胺的不对称炔基化反应

Scheme 39. Asymmetric alkynylation of isatin-derived ketimines

图式40. 1-烷基环状偶氮甲碱亚胺的不对称炔基化反应

Scheme 40. Catalytic asymmetric alkynylation of 1-alkyl C,N- cyclic azomethine imines

图式41. α,α-二芳基环状酮亚胺的不对称炔基化反应

Scheme 41. Cu-catalyzed enantioselective alkynylation of α,α-diaryl ketimines

图式42. N-酰基环状三氟甲基酮亚胺的不对称炔基化反应

Scheme 42. Catalytic asymmetric alkynylation of cyclic N-acyl trifluoromethyl ketimines

图式43. N-磺酰基酮酸酯亚胺的不对称炔基化反应

Scheme 43. Asymmetric alkynylation of cyclic N-sulfonyl ketimines

参考文献 52

[1]	Lauder K.; Toscani A.; Scalacci N.; Castagnolo D. Chem. Rev. 2017, 117, 14091. doi: 10.1021/acs.chemrev.7b00343
[2]	(a) Lu G.; Li Y.-M.; Li X.-S.; Chan A. S. C.Coord. Chem. Rev. 2005, 249, 1736. doi: 10.1016/j.ccr.2004.12.020 pmid: 248DAAE2-925A-4E47-9F71-0E1AF9A421D2
	(b) Blay G.; Monleón A.; Pedro J.R. Curr. Org. Chem. 2009, 13, 1498. doi: 10.2174/138527209789177734 pmid: 248DAAE2-925A-4E47-9F71-0E1AF9A421D2
	(c) Bian Q.; Zhong J.; Hou S.; Wang M. Chin. J. Org. Chem. 2010, 30, 1261. (in Chinese) doi: 10.1002/cjoc.201200309 pmid: 248DAAE2-925A-4E47-9F71-0E1AF9A421D2
	边庆花, 钟江春, 侯士聪, 王敏, 有机化学, 2010, 30, 1261.). pmid: 248DAAE2-925A-4E47-9F71-0E1AF9A421D2
	(d) Cheng M.; Li B.-G.Chin. Synth. Chem. 2012, 20, 1. (in Chinese) pmid: 248DAAE2-925A-4E47-9F71-0E1AF9A421D2
	成明, 李伯刚, 合成化学, 2012, 20, 1.). pmid: 248DAAE2-925A-4E47-9F71-0E1AF9A421D2
	(e) Bisai V.; Singh V.K. Tetrahedron Lett. 2016, 57, 4771. doi: 10.1016/j.tetlet.2016.09.048 pmid: 248DAAE2-925A-4E47-9F71-0E1AF9A421D2
[3]	Yan W.; Li P.; Feng J.; Wang D.; Zhu S.; Jiang X.; Wang R. Tetrahedron : Asymmetry 2010, 21, 2037. doi: 10.1016/j.tetasy.2010.07.020
[4]	Blay G.; Ceballos E.; Monleon A.; Pedro J.R. Tetrahedron 2012, 68, 2128. doi: 10.1016/j.tet.2012.01.037
[5]	(a) Liu T.-L.; Zhang H.-X.; Zheng Y.; Yao Q.; Ma J.-A. Chem. Commun. 2012, 48, 12234. doi: 10.1039/c2cc37290h
	(b) Yang Z.-Y.; Liu T.-L.; Zheng Y.; Li S.; Ma J.-A. Eur. J. Org. Chem. 2015, 3905.
[6]	Blay G.; Brines A.; Monlen A.; Pedro J.R. Chem.-Eur. J. 2012, 18, 2440. doi: 10.1002/chem.201102909
[7]	Xie Z.; Liu X.; Liu L. Org. Lett. 2016, 18, 2982. doi: 10.1021/acs.orglett.6b01328
[8]	Luzung M.R.; Dixon D.D.; Ortiz A.; Guerrero C.A.; Ayers S.; Ho J.; Schmidt M.A.; Strotman N.A.; Eastgate M.D. J. Org. Chem. 2017, 82, 10715. doi: 10.1021/acs.joc.7b01882
[9]	(a) Campbell M.J.; Toste F.D. Chem. Sci. 2011, 2, 1369. pmid: 22712050
	(b) Ranjan A.; Mandal A.; Yerande S.G.; Dethe D.H. Chem. Commun. 2015, 51, 14215. doi: 10.1039/C5CC05549K pmid: 22712050
[10]	Hashimoto T.; Omote M.; Maruoka K. Angew. Chem., Int. Ed. 2011, 50, 8952. doi: 10.1002/anie.v50.38
[11]	Pappoppula M.; Cardoso F. S. P.; Garrett B.O.; Aaron A. Angew. Chem., Int. Ed. 2015, 54, 15202. doi: 10.1002/anie.201507848
[12]	Kou X.; Zhao Q.; Guan Z.-H. Org. Chem. Front. 2020, 7, 838.
[13]	Ren Y.-Y.; Wang Y.-Q.; Liu S. J. Org. Chem. 2014, 79, 11759. doi: 10.1021/jo5022037
[14]	Munck L.D.; Monleón A.; Vila C.; Muñoz M.C.; Pedro J.R. Org. Biomol. Chem. 2015, 13, 7393. doi: 10.1039/C5OB01012H
[15]	Munck L.D.; Monleón A.; Vila C.; Pedro J.R. Adv. Synth. Catal. 2017, 359, 1582. doi: 10.1002/adsc.v359.9
[16]	Yu J.; Li Z.; Jia K.; Jiang Z.; Liu M.; Su W. Tetrahedron Lett. 2013, 54, 2006. doi: 10.1016/j.tetlet.2013.02.007
[17]	Sun S.; Li C.; Floreancig P.E.; Lou H.; Liu L. Org. Lett. 2015, 17, 1684. doi: 10.1021/acs.orglett.5b00447
[18]	Sun S.; Liu L. Synthesis 2016, 48, 2627. doi: 10.1055/s-0035-1561421
[19]	Perepichka I.; Kundu S.; Hearne Z.; Li C.-J. Org. Biomol. Chem. 2015, 13, 447. doi: 10.1039/C4OB02138J
[20]	Huang T.; Liu X.; Lang J.; Xu J.; Lin L.; Feng X. ACS Catal. 2017, 7, 5654. doi: 10.1021/acscatal.7b01912
[21]	(a) Wei C.; Li C.-J. J. Am. Chem. Soc. 2002, 124, 5638. doi: 10.1021/ja026007t
	Wei C.; Mague J.T.; Li C.-J. Proc. Natl. Acad. Sci. U.S. A. 2004, 101, 5749.
	Selected reviews:.
	(c) Peshkov V.A.; Pereshivko O.P.; Van der Eycken, E.V.Chem. Soc. Rev. 2012, 41, 3790. doi: 10.1039/c2cs15356d
	(d) Rokade B.V.; Barker J.; Guiry P.J. Chem. Soc. Rev. 2019, 48, 4766. doi: 10.1039/C9CS00253G
	(e) Mo J.-N.; Su J.; Zhao J. Molecules 2019, 24, 1216. doi: 10.3390/molecules24071216
	(f) Jesin I.; Nandi G.C. Eur. J. Org. Chem. 2019, 2704.
[22]	Bisai V.; Suneja A.; Singh V.K. Angew. Chem., Int. Ed. 2014, 53, 10737. doi: 10.1002/anie.201405074
[23]	Das B.G.; Shah S.; Singh V.K. Org. Lett. 2019, 21, 4981. doi: 10.1021/acs.orglett.9b01507
[24]	Dhanasekaran S.; Kannaujiya V.K.; Biswas R.G.; Singh V.K. J. Org. Chem. 2019, 84, 3275. doi: 10.1021/acs.joc.8b03225
[25]	Li Z.; Jiang Z.; Su W. Green Chem. 2015, 17, 2330. doi: 10.1039/C5GC00079C
[26]	Gao X.-T.; Gan C.-C.; Liu S.-Y.; Zhou F.; Wu H.-H.; Zhou J. ACS Catal. 2017, 7, 8588. doi: 10.1021/acscatal.7b03370
[27]	(a) Nakamura S.; Hyodo K.; Nakamura Y.; Shibata N.; Toru T. Adv. Synth. Catal. 2008, 350, 1443. doi: 10.1002/adsc.v350:10
	(b) Liu H.; Du D.-M. Adv. Synth. Catal. 2009, 351, 489. doi: 10.1002/adsc.v351:4
[28]	Nakamura S.; Ohara M.; Nakamura Y.; Shibata N.; Toru T. Chem.-Eur. J. 2010, 16, 2360. doi: 10.1002/chem.v16:8
[29]	Ohara M.; Hara Y.; Ohnuki T.; Nakamura S. Chem.-Eur. J. 2014, 20, 8848.
[30]	Knöpfel T.E.; Aschwanden P.; Ichikawa T.; Watanabe T.; Carreira E.M. Angew. Chem., Int. Ed. 2004, 43, 5971. doi: 10.1002/anie.200461286
[31]	Huang X.; Ma S. Acc. Chem. Res. 2019, 52, 1301.
[32]	(a) Ye J.; Li S.; Chen B.; Fan W.; Kuang J.; Liu J.; Liu Y.; Miao B.; Wan B.; Wang Y.; Xie X.; Yu Q.; Yuan W.; Ma S. Org. Lett. 2012, 14, 1346. doi: 10.1021/ol300296k pmid: WOS:000459590400023
	(b) Liu Q.; Cao T.; Han Y.; Jiang X.; Tang Y.; Zhai Y.; Ma S. Synlett 2019, 30, 477. doi: 10.1055/s-0037-1611641 pmid: WOS:000459590400023
[33]	Fan W.; Ma S. Chem. Commun. 2013, 49, 10175. doi: 10.1039/c3cc45118f
[34]	Fan W.; Yuan W.; Ma S. Nat. Commun. 2014, 5, 1.
[35]	(a) Lin W.; Cao T.; Fan W.; Han Y.; Kuang J.; Luo H.; Miao B.; Tang X.; Yu Q.; Yuan W.; Zhang J.; Zhu C.; Ma S. Angew. Chem., Int. Ed. 2014, 53, 277.
	(b) Lin W.; Ma S. Org. Chem. Front. 2014, 1, 338. doi: 10.1039/c4qo00058g
	(c) Lin W.; Ma S. Org. Chem. Front. 2017, 4, 958. doi: 10.1039/C7QO00062F
[36]	Zhou S.; Tong R. Org. Lett. 2017, 19, 1594. doi: 10.1021/acs.orglett.7b00414
[37]	(a) Cardoso F. S. P.; Abboud K.A.; Aponick A. J. Am. Chem. Soc. 2013, 135, 14548. doi: 10.1021/ja407689a
	(b) Paioti P. H. S.; Abboud K.A.; Aponick A. J. Am. Chem. Soc. 2016, 138, 2150. doi: 10.1021/jacs.5b13387
[38]	(a) Paioti P. H. S.; Abboud K.A.; Aponick A. ACS Catal. 2017, 7, 2133. doi: 10.1021/acscatal.7b00133
	(b) Rokade B.V.; Guiry P.J. ACS Catal. 2017, 7, 2334. doi: 10.1021/acscatal.6b03427
	(c) Rokade B.V.; Guiry P.J. J. Org. Chem. 2019, 84, 5763. doi: 10.1021/acs.joc.9b00728
[39]	(a) Min C.; Mittal N.; Sun D.X.; Seidel D. Angew. Chem., Int. Ed. 2013, 52, 14084. doi: 10.1002/anie.201308196
	(b) Mittal N.; Sun D.X.; Seidel D. Org. Lett. 2014, 16, 1012. doi: 10.1021/ol403773a
[40]	Zhao C.; Seidel D. J. Am. Chem. Soc. 2015, 137, 4650. doi: 10.1021/jacs.5b02071
[41]	Huang G.; Yang J.; Zhang X. Chem. Commun. 2011, 47, 5587. doi: 10.1039/C1CC10403A
[42]	Huang G.; Yin Z.; Zhang X. Chem.-Eur. J. 2013, 19, 11992. doi: 10.1002/chem.201301479
[43]	Morisaki K.; Sawa M.; Nomaguchi J.-Y.; Morimoto H.; Takeuchi Y.; Mashima K.; Ohshima T. Chem.-Eur. J. 2013, 19, 8417. doi: 10.1002/chem.v19.26
[44]	Morisaki K.; Sawa M.; Yonesaki R.; Morimoto H.; Mashima K.; Ohshima T. J. Am. Chem. Soc. 2016, 138, 6194. doi: 10.1021/jacs.6b01590
[45]	Yin L.; Otsuka Y.; Takada H.; Mouri S.; Yazaki R.; Kumagai N.; Shibasaki M. Org. Lett. 2013, 698.
[46]	Takada H.; Kumagai N.; Shibasaki M. Org. Lett. 2015, 17, 4762. doi: 10.1021/acs.orglett.5b02300
[47]	Chen Q.; Xie L.; Li Z.; Tang Y.; Zhao P.; Lin L.; Feng X.; Liu X. Chem. Commun. 2018, 54, 678. doi: 10.1039/C7CC08920A
[48]	Dasgupta S.; Liu J.; Shoffler C.A.; Yap G. P. A.; Watson M.P. Org. Lett. 2016, 18, 6006. doi: 10.1021/acs.orglett.6b02787
[49]	Zhang F.-G.; Ma H.; Nie J.; Zheng Y.; Gao Q.; Ma J.-A. Adv. Synth. Catal. 2012, 354, 1422. doi: 10.1002/adsc.201100926
[50]	Zhang Y.; Nie J.; Zhang F.-G.; Ma J.-A. J. Fluorine Chem. 2018, 208, 1. doi: 10.1016/j.jfluchem.2018.01.008
[51]	Ling Z.; Singh S.; Xie F.; Wu L.; Zhang W. Chem. Commun. 2017, 53, 5364. doi: 10.1039/C7CC02159C
[52]	Liu R.-R.; Zhu L.; Hu J.-P.; Lu C.-J.; Gao J.-R.; Lan Y.; Jia Y.-X. Chem. Commun. 2017, 53, 5890. doi: 10.1039/C7CC01015J