Synthesis 2022; 54(22): 5017-5025
DOI: 10.1055/a-1834-2927
special topic
Aryne Chemistry in Synthesis

Synthesis of Multisubstituted Benzenes from Phenols via Multisubstituted Benzynes

Akira Nagai
a   Laboratory of Chemical Bioscience, Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University (TMDU), 2-3-10 Kanda-Surugadai, Chiyoda-ku, Tokyo 101-0062, Japan
,
Akihiro Kobayashi
a   Laboratory of Chemical Bioscience, Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University (TMDU), 2-3-10 Kanda-Surugadai, Chiyoda-ku, Tokyo 101-0062, Japan
b   Department of Biological Science and Technology, Faculty of Advanced Engineering, Tokyo University of Science, 6-3-1 Niijuku, Katsushika-ku Tokyo 125-8585, Japan
,
Yuki Sakata
a   Laboratory of Chemical Bioscience, Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University (TMDU), 2-3-10 Kanda-Surugadai, Chiyoda-ku, Tokyo 101-0062, Japan
,
Yasunori Minami
a   Laboratory of Chemical Bioscience, Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University (TMDU), 2-3-10 Kanda-Surugadai, Chiyoda-ku, Tokyo 101-0062, Japan
,
Keisuke Uchida
a   Laboratory of Chemical Bioscience, Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University (TMDU), 2-3-10 Kanda-Surugadai, Chiyoda-ku, Tokyo 101-0062, Japan
,
a   Laboratory of Chemical Bioscience, Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University (TMDU), 2-3-10 Kanda-Surugadai, Chiyoda-ku, Tokyo 101-0062, Japan
,
Suguru Yoshida
b   Department of Biological Science and Technology, Faculty of Advanced Engineering, Tokyo University of Science, 6-3-1 Niijuku, Katsushika-ku Tokyo 125-8585, Japan
› Author Affiliations
This work was supported by KAKENHI Grant Number JP19K05451 (C; S.Y.); Uehara Foundation (S.Y.); and the Japan Agency for Medical Research and Development (AMED) under Grant Number JP21am0101098 (Platform Project for Supporting Drug Discovery and Life Science Research, BINDS).


Abstract

A new method to synthesize multifunctionalized arenes from simple phenols through aryne intermediates is described. Multisubstituted aryne precursors were prepared from phenols by Ir-catalyzed C–H borylation, deborylthiolation, O-triflylation, S-oxidation, and further modification through ortho-deprotonation directed by the sulfoxide moiety. Various multisubstituted arenes were synthesized by transformations of highly functionalized aryne intermediates generated from the o-sulfinylaryl triflates.

Supporting Information



Publication History

Received: 17 March 2022

Accepted after revision: 25 April 2022

Accepted Manuscript online:
25 April 2022

Article published online:
09 June 2022

© 2022. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
  • References

    • 1a Arene Chemistry: Reaction Mechanisms and Methods for Aromatic Compounds. Mortier J. Wiley; New Jersey: 2016
    • 1b Privileged Scaffolds in Medicinal Chemistry: Design, Synthesis, Evaluation. Bräse S. RSC; Cambridge: 2016

      Selected recent examples, see:
    • 2a Seo H, Ohmori K, Suzuki K. Chem. Lett. 2011; 40: 744
    • 2b Suzuki S, Segawa Y, Itami K, Yamaguchi J. Nat. Chem. 2015; 7: 227
    • 2c Sarkar D, Gulevich AV, Melkonyan FS, Gevorgyan V. ACS Catal. 2015; 5: 6792
    • 2d Lungerich D, Reger D, Hölzel H, Riedel R, Martin MM. J. C, Hampel F, Jux N. Angew. Chem. Int. Ed. 2016; 55: 5602
    • 2e Park J, Lee J, Chang S. Angew. Chem. Int. Ed. 2017; 56: 4256
    • 2f Zhang XJ, Beaudry CM. Org. Lett. 2020; 22: 6086
    • 2g Grau BW, Dill M, Hampel F, Kahnt A, Jux N, Tsogoeva SB. Angew. Chem. Int. Ed. 2021; 60: 22307
    • 2h Nilova A, Sibbald PA, Valente EJ, Gonzalez-Montiel GA, Richardson HC, Brown KS, Cheong PH. Y, Stuart DR. Chem. Eur. J. 2021; 27: 7168
  • 3 Modern Aryne Chemistry. Biju AT. Wiley-VCH; Weinheim: 2021

    • For recent reviews on arynes, see:
    • 4a Tadross PM, Stoltz BM. Chem. Rev. 2012; 112: 3550
    • 4b Bhunia A, Yetra SR, Biju AT. Chem. Soc. Rev. 2012; 41: 3140
    • 4c Yoshida S, Hosoya T. Chem. Lett. 2015; 44: 1450
    • 4d Goetz AE, Shah TK, Garg NK. Chem. Commun. 2015; 51: 34
    • 4e Bhojgude SS, Bhunia A, Biju AT. Acc. Chem. Res. 2016; 49: 1658
    • 4f García-López J.-A, Greaney MF. Chem. Soc. Rev. 2016; 45: 6766
    • 4g Shi J, Li Y, Li Y. Chem. Soc. Rev. 2017; 46: 1707
    • 4h Idiris FI. M, Jones CR. Org. Biomol. Chem. 2017; 15: 9044
    • 4i Roy T, Biju A. Chem. Commun. 2018; 54: 2580
    • 4j Yoshida S. Bull. Chem. Soc. Jpn. 2018; 91: 1293
    • 4k Matsuzawa T, Yoshida S, Hosoya T. Tetrahedron Lett. 2018; 59: 4197
    • 4l Takikawa H, Nishii A, Sakai T, Suzuki K. Chem. Soc. Rev. 2018; 47: 8030
    • 4m Nakamura Y, Yoshida S, Hosoya T. Heterocycles 2019; 98: 1623
    • 4n Werz DB, Biju AT. Angew. Chem. Int. Ed. 2020; 59: 3385

      For recent aryne chemistry, see:
    • 5a Mizukoshi Y, Mikami K, Uchiyama M. J. Am. Chem. Soc. 2015; 137: 74
    • 5b García-López J.-A, Çetin M, Greaney MF. Angew. Chem. Int. Ed. 2015; 54: 2156
    • 5c Nathel NF. F, Morrill LA, Mayr H, Garg NK. J. Am. Chem. Soc. 2016; 138: 10402
    • 5d Umezu S, dos Passos Gomes G, Yoshinaga T, Sakae M, Matsumoto K, Iwata T, Alabugin I, Shindo M. Angew. Chem. Int. Ed. 2017; 56: 1298
    • 5e Shi J, Xu H, Qiu D, He J, Li Y. J. Am. Chem. Soc. 2017; 139: 623
    • 5f Kitamura T, Gondo K, Oyamada J. J. Am. Chem. Soc. 2017; 139: 8416
    • 5g Zhou M, Ni C, Zeng Y, Hu J. J. Am. Chem. Soc. 2018; 140: 6801
    • 5h Xiao X, Hoye TR. Nat. Chem. 2018; 10: 838
    • 5i Mesgar M, Nguyen-Le J, Daugulis O. J. Am. Chem. Soc. 2018; 140: 13703
    • 5j Gaykar RN, Guin A, Bhattacharjee S, Biju AT. Org. Lett. 2019; 21: 9613
    • 5k Nishii A, Takikawa H, Suzuki K. Chem. Sci. 2019; 10: 3840
    • 5l Tanaka H, Osaka I, Yoshida H. Chem. Lett. 2019; 48: 1032
    • 5m Fujimoto H, Kusano M, Kodama T, Tobisu M. Org. Lett. 2020; 22: 2293
    • 5n Haas TM, Wiesler S, Dürr-Mayer T, Ripp A, Fouka P, Qiu D, Jessen HJ. Angew. Chem. Int. Ed. 2022; 61: e202113231
    • 5o Ikawa T, Yamamoto Y, Heguri A, Fukumoto Y, Murakami T, Takagi A, Masuda Y, Yahata K, Aoyama H, Shigeta Y, Tokiwa H, Akai S. J. Am. Chem. Soc. 2021; 143: 10853
    • 5p Jančařík A, Holec J, Nagata Y, Šámal M, Gourdon A. Nat. Commun. 2022; 13: 223

      For our recent aryne chemistry, see:
    • 6a Kobayashi T, Hosoya T, Yoshida S. J. Org. Chem. 2020; 85: 4448
    • 6b Kanemoto K, Sakata Y, Hosoya T, Yoshida S. Chem. Lett. 2020; 49: 593
    • 6c Kobayashi T, Hosoya T, Yoshida S. Chem. Lett. 2020; 49: 809
    • 6d Matsuzawa T, Hosoya T, Yoshida S. Chem. Sci. 2020; 11: 9691
    • 6e Nakamura Y, Sakata Y, Hosoya T, Yoshida S. Org. Lett. 2020; 22: 8505
    • 6f Nakajima H, Hazama Y, Sakata Y, Uchida K, Hosoya T, Yoshida S. Chem. Commun. 2021; 57: 2621
    • 6g Minoshima M, Uchida K, Nakamura Y, Hosoya T, Yoshida S. Org. Lett. 2021; 23: 1868
    • 6h Kobayashi T, Hosoya T, Yoshida S. Bull. Chem. Soc. Jpn. 2021; 94: 1823
    • 7a Bronner SM, Goetz AE, Garg NK. J. Am. Chem. Soc. 2011; 133: 3832
    • 7b Picazo E, Houk KN, Garg NK. Tetrahedron Lett. 2015; 56: 3511
  • 8 Yoshida S, Uchida K, Hosoya T. Chem. Lett. 2014; 43: 116
  • 9 Boebel TA, Hartwig JF. J. Am. Chem. Soc. 2008; 130: 7534
    • 10a Yoshida S, Sugimura Y, Hazama Y, Nishiyama Y, Yano T, Shimizu S, Hosoya T. Chem. Commun. 2015; 51: 16613
    • 10b Kanemoto K, Sugimura Y, Shimizu S, Yoshida S, Hosoya T. Chem. Commun. 2017; 53: 10640
    • 10c Kanemoto K, Yoshida S, Hosoya T. Chem. Lett. 2018; 47: 85
  • 11 Rauhut CB, Melzig L, Knochel P. Org. Lett. 2008; 10: 3891
    • 12a Wender PA, Holt DA. J. Am. Chem. Soc. 1985; 107: 7771
    • 12b Brummond KM, Gesenberg KD. Tetrahedron Lett. 1999; 40: 2231
    • 13a Reynolds GA. J. Org. Chem. 1964; 29: 3733
    • 13b Shi F, Waldo JP, Chen Y, Larock RC. Org. Lett. 2008; 10: 2409
  • 14 Yoshida H, Shirakawa E, Honda Y, Hiyama T. Angew. Chem. Int. Ed. 2002; 41: 3247
    • 15a Chen J, Li J, Plutschack MB, Berger F, Ritter T. Angew. Chem. Int. Ed. 2020; 59: 5616
    • 15b Jia H, Häring AP, Berger F, Zhang L, Ritter T. J. Am. Chem. Soc. 2021; 143: 7623
  • 16 Nakamura Y, Miyata Y, Uchida K, Yoshida S, Hosoya T. Org. Lett. 2019; 21: 5252
  • 17 Matsuzawa T, Uchida K, Yoshida S, Hosoya T. Chem. Lett. 2018; 47: 825
  • 18 Medina JM, Mackey JL, Garg NK, Houk KN. J. Am. Chem. Soc. 2014; 136: 15798