Enantioselective Synthesis of Axially Chiral Benzimidazoles ­Bearing a C–N axis via Pd-Catalyzed Buchwald–Hartwig ­Amination

Abstract

Benzimidazole atropisomers bearing a C–N axis are privileged structural frameworks in pharmaceutical and natural products, thus appealing an increasing interest for its asymmetric synthesis. Here, we briefly discuss recent advances in the asymmetric synthesis of benzimidazole atropisomers with a C–N axis, with particular attention to our recently developed palladium-catalyzed intramolecular Buchwald–Hartwig amination strategy.

Key words

atropisomerism - palladium - amination - benzimidazole atropisomers - asymmetric catalysis

Publication History

Received: 12 April 2022

Accepted after revision: 23 April 2022

Accepted Manuscript online:
25 April 2022

Article published online:
19 May 2022

• References

• 1a Tang W, Zhang X. Chem. Rev. 2003; 103: 3029
• 1b Bringmann G, Gulder T, Gulder TA. M, Breuning M. Chem. Rev. 2011; 111: 563
• 1c Smyth JE, Butler NM, Keller PA. Nat. Prod. Rep. 2015; 32: 1562
• 1d Wencel-Delord J, Colobert F. SynOpen 2020; 4: 107
• 1e Shao Y.-D, Cheng D.-J. ChemCatChem 2021; 13: 1271
• 2 Christie GH, Kenner J. J. Chem. Soc., Trans. 1922; 120: 614
• 3a Wencel-Delord J, Panossian A, Leroux FR, Colobert F. Chem. Soc. Rev. 2015; 44: 3418
• 3b Wang YB, Tan B. Acc. Chem. Res. 2018; 51: 534
• 3c Link A, Sparr C. Chem. Soc. Rev. 2018; 47: 3804
• 3d Cheng JK, Xiang SH, Li S, Ye L, Tan B. Chem. Rev. 2021; 121: 4805
• 4a Rodríguez-Salamanca P, Fernández R, Hornillos V, Lassaletta JM. Chem. Eur. J. 2022; 28: e202104442; DOI: DOI: 10.1002/chem.202104442.
• 4b Zhang Y.-C, Jiang F, Shi F. Acc. Chem. Res. 2020; 53: 425
• 4c Colobert F, Shi B.-F. Chem. Catal. 2021; 1: 483
• 5a Bock LH, Adams R. J. Am. Chem. Soc. 1931; 53: 374
• 5b Bock LH, Adams R. J. Am. Chem. Soc. 1931; 53: 3519
• 6a Kamikawa K, Kinoshita S, Matsuzaka H, Uemura M. Org. Lett. 2006; 8: 1097
• 6b Kamikawa K, Kinoshita S, Furusyo M, Takemoto S, Matsuzaka H, Uemura M. J. Org. Chem. 2007; 72: 3394
• 7a Wang Y, Zheng S, Hu Y, Tan B. Nat. Commun. 2017; 8: 15489
• 7b Zhang L, Zhang J, Ma J, Cheng DJ, Tan B. J. Am. Chem. Soc. 2017; 139: 1714
• 7c Kwon Y, Li J, Reid JP, Crawford JM, Jacob R, Sigman MS, Toste FD, Miller SJ. J. Am. Chem. Soc. 2019; 141: 6698
• 7d Wang L, Zhong J, Lin X. Angew. Chem. Int. Ed. 2019; 58: 15824
• 7e Xia W, An Q.-J, Xiang S.-H, Li S, Wang Y.-B, Tan B. Angew. Chem. Int. Ed. 2020; 59: 6775
• 7f Kim A, Kim A, Park S, Kim S, Jo H, Ok KM, Lee SK, Song J, Kwon Y. Angew. Chem. Int. Ed. 2021; 60: 12279
• 8a Ye C.-X, Chen S, Han F, Xie X, Ivlev S, Houk KN, Meggers E. Angew. Chem. Int. Ed. 2020; 59: 13552
• 8b Zhang S, Yao Q.-J, Liao G, Li X, Li H, Chen H.-M, Hong X, Shi B.-F. ACS Catal. 2019; 9: 1956
• 8c Ren Q, Cao T, He C, Yang M, Liu H, Wang L. ACS Catal. 2021; 11: 6135
• 8d Dhawa U, Tian C, Wdowik T, Oliveira JC. A, Hao J, Ackermann L. Angew. Chem. Int. Ed. 2020; 59: 13451
• 9a Ototake N, Morimoto Y, Mokuya A, Fukaya H, Shida Y, Kitagawa O. Chem. Eur. J. 2010; 16: 6752
• 9b Morimoto Y, Shimizu S, Mokuya A, Ototake N, Saito A, Kitagawa O. Tetrahedron 2016; 72: 5221
• 9c Sun L, Chen H, Liu B, Chang J, Kong L, Wang F, Lan Y, Li X. Angew. Chem. Int. Ed. 2021; 60: 8391
• 10a Zhao Y, Xia W. Chem. Soc. Rev. 2018; 47: 2591
• 10b Lanzi M, Merad J, Boyarskaya DV, Maestri G, Allain C, Masson G. Org. Lett. 2018; 20: 5247
• 10c Lagishetti C, Kiran IN. C, You H, He Y. Org. Lett. 2016; 18: 3818
• 10d Reddy RS, Reddy RS, Zheng S, Lagishetti C, You H, He Y. RSC Adv. 2016; 6: 68199
• 10e Shin K, Kim H, Chang S. Acc. Chem. Res. 2015; 48: 1040
• 10f Bariwalab J, Van der Eycken E. Chem. Soc. Rev. 2013; 42: 9283
• 11a Dorel R, Grugel CP, Haydl AM. Angew. Chem. Int. Ed. 2019; 58: 17118
• 11b Louie J, Hartwig JF. Tetrahedron Lett. 1995; 36: 3609
• 11c Guram AS, Rennels RA, Buchwald SL. Angew. Chem., Int. Ed. Engl. 1995; 34: 1348
• 11d Guram AS, Buchwald SL. J. Am. Chem. Soc. 1994; 116: 7901
• 11e Paul F, Patt J, Hartwig JF. J. Am. Chem. Soc. 1994; 116: 5969
• 12a Dai L. Prog. Chem. 2018; 30: 1295
• 12b You H, Vegi SR, Lagishetti C, Chen S, Reddy RS, He Y. J. Org. Chem. 2018; 83: 4119
• 12c De S, Yin JMa D. Org. Lett. 2017; 19: 4864
• 12d Bhunia S, Pawar GG, Kumar S, Jiang Y, Ma D. Angew. Chem. Int. Ed. 2017; 56: 16136
• 12e Fan M, Zhou W, Jiang Y, Ma D. Org. Lett. 2015; 17: 5934
• 12f Sambiagio C, Marsden SP, Blacker AJ, McGowan PC. Chem. Soc. Rev. 2014; 43: 3525
• 13a Hirata T, Takahashi I, Suzuki Y, Yoshida H, Hasegawa H, Kitagawa O. J. Org. Chem. 2016; 81: 318
• 13b Kitagawa O, Takahashi M, Yoshikawa M, Taguchi T. J. Am. Chem. Soc. 2005; 127: 3676
• 13c Kitagawa O, Yoshikawa M, Tanabe H, Morita T, Takahashi M, Dobashi Y, Taguchi T. J. Am. Chem. Soc. 2006; 128: 12923
• 14a Fan XZhang X. Li C, Gu Z. ACS Catal. 2019; 9: 2286
• 14b Zhao K, Duan L, Xu S, Jiang J, Fu Y, Gu Z. Chem 2018; 4: 599
• 14c Zhao K, Yang S, Gong Q, Duan L, Gu Z. Angew. Chem. Int. Ed. 2021; 60: 5788
• 15a Rae J, Frey J, Jerhaoui S, Choppin S, Wencel-Delord J, Colobert F. ACS Catal. 2018; 8: 2805
• 15b Frey J, Malekafzali A, Delso I, Choppin S, Colobert F, Wencel-Delord J. Angew. Chem. Int. Ed. 2020; 59: 8844
• 16a Bringmann G, Tasler S, Endress H, Kraus J, Messer K, Wohlfarth M, Lobin W. J. Am. Chem. Soc. 2001; 123: 2703
• 16b Hughes CC, Prieto-Davo A, Jensen PR, Fenical W. Org. Lett. 2008; 10: 629
• 16c Toenjes ST, Gustafson JL. Future Med. Chem. 2018; 10: 409
• 16d LaPlante SR, Fader LD, Fandrick KR, Fandrick DR, Hucke O, Kemper R, Miller SP. F, Edwards PJ. J. Med. Chem. 2011; 54: 7005
• 16e Kriegelstein M, Profous D, Lyčka A, Travnícek Z, Přibylka A, Volná T, Benická S, Cankař P. J. Org. Chem. 2019; 84: 11911
• 17 Kwon Y, Li J, Reid JP, Crawford JM, Jacob R, Sigman MS, Toste FD, Miller SJ. J. Am. Chem. Soc. 2019; 141: 6698
• 18 Man N, Lou Z, Li Y, Yang H, Zhao Y, Fu H. Org. Lett. 2020; 22: 6382
• 19 An Q.-J, Xia W, Ding W.-Y, Liu H.-H, Xiang S.-H, Wang Y.-B, Zhong G, Tan B. Angew. Chem. Int. Ed. 2021; 60: 24888
• 20 Zhang P, Wang X.-M, Xu Qi, Guo C.-Q, Wang P, Lu C.-J, Liu R.-R. Angew. Chem. Int. Ed. 2021; 60: 21718