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Synthesis 2022; 54(21): 4734-4752
DOI: 10.1055/a-1677-5870
special topic
Asymmetric C–H Functionalization

Recent Advances on Transition-Metal-Catalyzed Asymmetric C–H Arylation Reactions

Mingliang Li
a   Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055, P. R. of China
,
Jun Wang  ∗
a   Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055, P. R. of China
b   Department of Chemistry, Hong Kong Baptist University, Kowloon, Hong Kong, China
› Author AffiliationsThis work was supported by the National Natural Science Foundation of China (NSFC 21902072).
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Abstract

Transition-metal-catalyzed asymmetric C–H functionalization has become a powerful strategy to synthesize complex chiral molecules. Recently, catalytic enantioselective C–H arylation has attracted great interest from organic chemists to construct aryl-substituted chiral compounds. In this short review, we highlight recent advances in asymmetric C–H arylation from 2019 to late 2021, including enantioselective C(sp2)–H arylation to construct axial or planar chiral compounds, and enantioselective C(sp3)–H arylation to introduce central chirality via desymmetrization of the methyl group or methylene C–H activation. These processes proceed with palladium, rhodium, iridium, nickel, or copper catalysts, and utilize aryl halides, boron, or diazo derivatives as arylation reagents.

1 Introduction

2 Transition-Metal-Catalyzed Asymmetric C(sp2)–H Arylation

2.1 Chelation-Assisted Asymmetric C(sp2)–H Arylation for the Construction of Atropisomer

2.2 Chelation-Assisted Asymmetric C(sp2)–H Arylation for the Construction of Planar Chiral Compounds

2.3 Chelation-Assisted Asymmetric C(sp2)–H Arylation and Axial-to-Central Chirality Transfer for the Construction of Spirocycles

2.4 Other Asymmetric C(sp2)–H Arylation Reactions

3 Transition-Metal-Catalyzed Asymmetric C(sp3)–H Arylation

3.1 Chelation-Assisted Enantioselective C(sp3)–H Arylation through Desymmetrization

3.2 Chelation-Assisted Enantioselective Methylene C(sp3)–H Aryl­ation

3.3 Other Asymmetric C(sp3)–H Arylations

4 Conclusion and Outlook

Key words

C–H bond functionalization - transition-metal catalysis - asymmetric C–H activation - C(sp2)–H arylation - C(sp3)–H arylation - aryl­ation - chiral ligands


Publication History

Received: 26 September 2021

Accepted after revision: 25 October 2021

Accepted Manuscript online:
25 October 2021

Article published online:
14 December 2021

© 2021. Thieme. All rights reserved

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  • References


      • For selected reviews, see:
    • 1a Ackermann L, Vicente R, Kapdi AR. Angew. Chem. Int. Ed. 2009; 48: 9792
      CrossrefPubMed
    • 1b Kuhl N, Hopkinson MN, Wencel-Delord J, Glorius F. Angew. Chem. Int. Ed. 2012; 51: 10236
      CrossrefPubMed
    • 1c Dong Z, Ren Z, Thompson SJ, Xu Y, Dong G. Chem. Rev. 2017; 117: 9333
      CrossrefPubMed
    • 1d Park Y, Kim Y, Chang S. Chem. Rev. 2017; 117: 9247
      CrossrefPubMed
    • 1e Leitch JA, Frost CG. Chem. Soc. Rev. 2017; 46: 7145
      CrossrefPubMed
    • 1f He J, Wasa M, Chan KS. L, Shao Q, Yu J.-Q. Chem. Rev. 2017; 117: 8754
      CrossrefPubMed
    • 1g Chu JC. K, Rovis T. Angew. Chem. Int. Ed. 2018; 57: 62
      CrossrefPubMed
    • 1h Gandeepan P, Ackermann L. Chem 2018; 4: 199
      CrossrefPubMed

      For selected reviews, see:
    • 2a Yamaguchi J, Yamaguchi AD, Itami K. Angew. Chem. Int. Ed. 2012; 51: 8960
      CrossrefPubMed
    • 2b Wencel-Delord J, Glorius F. Nat. Chem. 2013; 5: 369
      CrossrefPubMed
    • 2c Ackermann L. Org. Process Res. Dev. 2015; 19: 260
      Crossref
    • 2d Seki M. Org. Process Res. Dev. 2016; 20: 867
      Crossref
    • 2e Basu D, Kumar S, Sai Sudhir V, Bandichhor R. J. Chem. Sci. 2018; 130: 71
      Crossref
    • 2f Baudoin O. Angew. Chem. Int. Ed. 2020; 59: 17798
      CrossrefPubMed
  • 3 Hartwig JF, Larsen MA. ACS Cent. Sci. 2016; 2: 281
    CrossrefPubMed

      • For selected reviews, see:
    • 4a Neufeldt SR, Sanford MS. Acc. Chem. Res. 2012; 45: 936
      CrossrefPubMed
    • 4b Rouquet G, Chatani N. Angew. Chem. Int. Ed. 2013; 52: 11726
      CrossrefPubMed
    • 4c Daugulis O, Roane J, Tran LD. Acc. Chem. Res. 2015; 48: 1053
      CrossrefPubMed
    • 4d Dey A, Maity S, Maiti D. Chem. Commun. 2016; 52: 12398
      CrossrefPubMed
    • 4e Dey A, Sinha SK, Achar TK, Maiti D. Angew. Chem. Int. Ed. 2019; 58: 10820
      CrossrefPubMed
    • 4f Meng G, Lam NY. S, Lucas EL, Saint-Denis TG, Verma P, Chekshin N, Yu J.-Q. J. Am. Chem. Soc. 2020; 142: 10571
      CrossrefPubMed

      For selected reviews, see:
    • 5a Moir M, Danon JJ, Reekie TA, Kassiou M. Expert Opin. Drug Discovery 2019; 14: 1137
      CrossrefPubMed
    • 5b Börgel J, Ritter T. Chem 2020; 6: 1877
      CrossrefPubMed
    • 5c Kelly CB, Padilla-Salinas R. Chem. Sci. 2020; 11: 10047
      CrossrefPubMed
  • 6 Carey JS, Laffan D, Thomson C, Williams MT. Org. Biomol. Chem. 2006; 4: 2337
    CrossrefPubMed

      • For selected reviews, see:
    • 7a Zheng C, You S.-L. RSC Adv. 2014; 4: 6173
      CrossrefPubMed
    • 7b Pellissier H, Clavier H. Chem. Rev. 2014; 114: 2775
      CrossrefPubMed
    • 7c Wang F, Chen P, Liu G. Acc. Chem. Res. 2018; 51: 2036
      CrossrefPubMed
    • 7d Pellissier H. Coord. Chem. Rev. 2019; 386: 1
      Crossref

      For selected examples, see:
    • 8a Groves JT, Viski P. J. Am. Chem. Soc. 1989; 111: 8537
      Crossref
    • 8b Burg F, Breitenlechner S, Jandl C, Bach T. Chem. Sci. 2020; 11: 2121
      CrossrefPubMed

      For selected examples, see:
    • 9a DeAngelis A, Shurtleff VM, Dmitrenko O, Fox JM. J. Am. Chem. Soc. 2011; 133: 1650
      CrossrefPubMed
    • 9b Liao K, Negretti S, Musaev DG, Bacsa J, Davies HM. L. Nature 2016; 533: 230
      CrossrefPubMed

      For selected reviews, see:
    • 10a Newton CG, Wang S.-G, Oliveira CC, Cramer N. Chem. Rev. 2017; 117: 8908
      CrossrefPubMed
    • 10b Saint-Denis TG, Zhu R.-Y, Chen G, Wu Q.-F, Yu J.-Q. Science 2018; 359: eaao4798
      CrossrefPubMed
    • 10c Diesel J, Cramer N. ACS Catal. 2019; 9: 9164
      Crossref
    • 10d Shao Q, Wu K, Zhuang Z, Qian S, Yu J.-Q. Acc. Chem. Res. 2020; 53: 833
      CrossrefPubMed
    • 10e Thongpaen J, Manguin R, Baslé O. Angew. Chem. Int. Ed. 2020; 59: 10242
      CrossrefPubMed
    • 10f Yang K, Song M, Liu H, Ge H. Chem. Sci. 2020; 11: 12616
      CrossrefPubMed
    • 10g Liao G, Zhang T, Lin Z.-K, Shi B.-F. Angew. Chem. Int. Ed. 2020; 59: 19773
      CrossrefPubMed
    • 10h Liu C.-X, Gu Q, You S.-L. Trends Chem. 2020; 2: 737
      Crossref
    • 10i Achar TK, Maiti S, Jana S, Maiti D. ACS Catal. 2020; 10: 13748
      Crossref
    • 10j Liu W, Ke J, He C. Chem. Sci. 2021; 12: 10972
      CrossrefPubMed
    • 10k Liu C.-X, Zhang W.-W, Yin S.-Y, Gu Q, You S.-L. J. Am. Chem. Soc. 2021; 143: 14025
      CrossrefPubMed
  • 11 Wang Q, Cai Z.-J, Liu C.-X, Gu Q, You S.-L. J. Am. Chem. Soc. 2019; 141: 9504
    CrossrefPubMed
  • 12 Wang Q, Zhang W.-W, Song H, Wang J, Zheng C, Gu Q, You S.-L. J. Am. Chem. Soc. 2020; 142: 15678
    CrossrefPubMed
  • 13 Feng J, Gu Z. SynOpen 2021; 5: 68
    Article in Thieme ConnectPubMed
  • 14 Jin L, Yao Q.-J, Xie P.-P, Li Y, Zhan B.-B, Han Y.-Q, Hong X, Shi B.-F. Chem 2020; 6: 497
    CrossrefPubMed
  • 15 Yang C, Wu T.-R, Li Y, Wu B.-B, Jin R.-X, Hu D.-D, Li Y.-B, Bian K.-J, Wang X.-S. Chem. Sci. 2021; 12: 3726
    CrossrefPubMed
  • 16 Pan C, Yin S.-Y, Wang S.-B, Gu Q, You S.-L. Angew. Chem. Int. Ed. 2021; 60: 15510
    CrossrefPubMed
  • 17 Woźniak Ł, Cramer N. Angew. Chem. Int. Ed. 2021; 60: 18532
    CrossrefPubMed
  • 18 Cai Z.-J, Liu C.-X, Gu Q, Zheng C, You S.-L. Angew. Chem. Int. Ed. 2019; 58: 2149
    CrossrefPubMed
  • 19 Cai Z.-J, Liu C.-X, Wang Q, Gu Q, You S.-L. Nat. Commun. 2019; 10: 4168
    CrossrefPubMed
  • 20 Liu C.-X, Cai Z.-J, Wang Q, Wu Z.-J, Gu Q, You S.-L. CCS Chem. 2020; 2: 642
    CrossrefPubMed
  • 21 Kong L, Han X, Liu S, Zou Y, Lan Y, Li X. Angew. Chem. Int. Ed. 2020; 59: 7188
    CrossrefPubMed
  • 22 Batuecas M, Luo J, Gergelitsová I, Krämer K, Whitaker D, Vitorica-Yrezabal IJ, Larrosa I. ACS Catal. 2019; 9: 5268
    CrossrefPubMed
  • 23 Nguyen Q.-H, Guo S.-M, Royal T, Baudoin O, Cramer N. J. Am. Chem. Soc. 2020; 142: 2161
    CrossrefPubMed
  • 24 Savary D, Baudoin O. Angew. Chem. Int. Ed. 2021; 60: 5136
    CrossrefPubMed
  • 25 Jiang H.-J, Zhong X.-M, Liu Z.-Y, Geng R.-L, Li Y.-Y, Wu Y.-D, Zhang X, Gong L.-Z. Angew. Chem. Int. Ed. 2020; 59: 12774
    CrossrefPubMed
  • 26 Saint-Denis TG, Lam NY. S, Chekshin N, Richardson PF, Chen JS, Elleraas J, Hesp KD, Schmitt DC, Lian Y, Huh CW, Yu J.-Q. ACS Catal. 2021; 11: 9738
    CrossrefPubMed
  • 27 Jerhaoui S, Djukic J.-P, Wencel-Delord J, Colobert F. ACS Catal. 2019; 9: 2532
    CrossrefPubMed
  • 28 Zhuang Z, Yu J.-Q. J. Am. Chem. Soc. 2020; 142: 12015
    CrossrefPubMed
  • 29 Han Y.-Q, Yang X, Kong K.-X, Deng Y.-T, Wu L.-S, Ding Y, Shi B.-F. Angew. Chem. Int. Ed. 2020; 59: 20455
    CrossrefPubMed
  • 30 Han Y.-Q, Zhang Q, Yang X, Jiang M.-X, Ding Y, Shi B.-F. Org. Lett. 2021; 23: 97
    CrossrefPubMed
  • 31 Yang X, Jiang M.-X, Zhou T, Han Y.-Q, Xu X.-T, Zhang K, Shi B.-F. Chem. Commun. 2021; 57: 5562
    CrossrefPubMed
  • 32 Xiao L.-J, Hong K, Luo F, Hu L, Ewing WR, Yeung K.-S, Yu J.-Q. Angew. Chem. Int. Ed. 2020; 59: 9594
    CrossrefPubMed
  • 33 Zhang W, Wu L, Chen P, Liu G. Angew. Chem. Int. Ed. 2019; 58: 6425
    CrossrefPubMed
  • 34 Cheng X, Lu H, Lu Z. Nat. Commun. 2019; 10: 3549
    CrossrefPubMed
  • 35 Kong W.-X, Xie S.-J, Cao C.-Y.-Z, Zhang C.-W, Wang C, Duan W.-L. Chem. Commun. 2020; 56: 2292
    CrossrefPubMed
  • 36 Melot R, Zuccarello M, Cavalli D, Niggli N, Devereux M, Bgrgi T, Baudoin O. Angew. Chem. Int. Ed. 2021; 60: 7245
    CrossrefPubMed