Photocatalyzed C–F Bond Heteroarylation of Trifluoromethyl­arenes with Heteroarenes: Two Roles of Bu3SnI as Fluoride Ion Scavenger and Activator for Photocatalyst

Naoki Sugihara; Masayuki Abe; Yoshihiro Nishimoto; Makoto Yasuda

doi:10.1055/a-2235-1380

Synthesis, Table of Contents

Synthesis 2024; 56(21): 3297-3306
DOI: 10.1055/a-2235-1380

paper

Special Issue PSRC-10 (10th Pacific Symposium on Radical Chemistry)

Photocatalyzed C–F Bond Heteroarylation of Trifluoromethylarenes with Heteroarenes: Two Roles of Bu₃SnI as Fluoride Ion Scavenger and Activator for Photocatalyst

Naoki Sugihara

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

,

Masayuki Abe

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

,

Yoshihiro Nishimoto ∗

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

^bInnovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan

,

Makoto Yasuda ∗

^aDepartment of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

^bInnovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan

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Abstract

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Abstract

We report the C–F bond heteroarylation of trifluoromethylarenes with heteroarenes by using Ir(ppy)₃ catalyst and Bu₃SnI under visible-light irradiation. Various heteroarenes such as pyrrole, furan, and thiophene derivatives were applied to the present reaction. The present heteroarylation enables the transformation of various functionalized trifluoromethylarenes because of the mild reaction conditions. Notably, the late-stage transformation of a drug molecule, bicalutamide, was demonstrated. Mechanistic studies including a light on–off interval experiment, Stern–Volmer luminescence-quenching measurements, and DFT calculations clarified two critical roles of Bu₃SnI for the successful progress of the heteroarylation. Bu₃SnI functions as a fluoride ion scavenger to suppress the undesired C–F bond re-formation. Bu₃SnI also acts as a single-electron source for the reduction of photoexcited Ir(ppy)₃* to generate Ir(II) species to effectively reduce ArCF₃.

Key words

C–F bond transformation - diaryldifluoromethanes - heteroarylation - photocatalysis - organostannanes - pyrroles - furans - thiophenes

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References

References

Selected reviews:

1a Blackburn GM, England DA, Kolkmann F. J. Chem. Soc., Chem. Commun. 1981; 930
1b Blackburn GM, Kent DE, Kolkmann F. J. Chem. Soc., Perkin Trans. 1 1984; 1119
1c Gillis EP, Eastman KJ, Hill MD, Donnelly DJ, Meanwell NA. J. Med. Chem. 2015; 58: 8315
1d Meanwell NA. J. Med. Chem. 2018; 61: 5822
1e Johnson BM, Shu Y.-Z, Zhuo X, Meanwell NA. J. Med. Chem. 2020; 63: 6315

Reports on the synthesis of diaryldifluoromethanes without use of ArCF₃ as a starting material:

2a Chang Y, Tewari A, Adi AI, Bae C. Tetrahedron 2008; 64: 9837
2b Gu JW, Guo WH, Zhang X. Org. Chem. Front. 2015; 2: 38
2c Nambo M, Yim JC. H, Freitas LB. O, Tahara Y, Ariki ZT, Maekawa Y, Yokogawa D, Crudden C. Nat. Commun. 2019; 10: 4528
2d Geri JB, Wolfe MM. W, Szymczak NK. J. Am. Chem. Soc. 2018; 140: 9404
2e Bunnell A, Lalloo N, Brigham C, Sanford MS. Org. Lett. 2023; 25: 7584

Selected reviews:

3a Wang J, Sánchez-Roselló M, Aceña JL, Pozo C, Sorochinsky AE, Fustero S, Soloshonok VA, Liu H. Chem. Rev. 2014; 114: 2432
3b Zhou Y, Wang J, Gu Z, Wang S, Zhu W, Aceña JL, Soloshonok VA, Izawa K, Liu H. Chem. Rev. 2016; 116: 422

Selected reviews:

4a Tomashenko OA, Grushin VV. Chem. Rev. 2011; 111: 475
4b Furuya T, Kamlet AS, Ritter T. Nature 2011; 473: 470
4c Besset T, Schneider C, Cahard D. Angew. Chem. Int. Ed. 2012; 51: 5048
4d Alonso C, de Marigorta EM, Rubiales G, Palacios F. Chem. Rev. 2015; 115: 1847
4e Barata-Vallejo S, Lantaño B, Postigo A. Chem. Eur. J. 2014; 20: 16806
4f Xiao H, Zhang Z, Fang Y, Zhu L, Li C. Chem. Soc. Rev. 2021; 50: 6308
4g Mandal D, Maji S, Pal T, Sinha SK, Maiti D. Chem. Commun. 2022; 58: 10442

5a Yoshida S, Shimomori K, Kim Y, Hosoya T. Angew. Chem. Int. Ed. 2016; 55: 10406
5b Mandal D, Gupta R, Jaiswal AK, Young RD. J. Am. Chem. Soc. 2020; 142: 2572
5c Cabrera-Trujillo JJ, Fernández I. Chem. Eur. J. 2021; 27: 3823
5d Kako M, Morita T, Torihara T, Nakadaira Y. J. Chem. Soc., Chem. Commun. 1993; 678
5e Clavel P, Lessene G, Biran C, Bordeau M, Roques N, Trévin S, de Montauzon D. J. Fluorine Chem. 2001; 107: 301
5f Amii H, Hatamoto Y, Seo M, Uneyama K. J. Org. Chem. 2001; 66: 7216
5g Luo C, Bandar JS. J. Am. Chem. Soc. 2019; 141: 14120
5h Chen K, Berg N, Gschwind R, König B. J. Am. Chem. Soc. 2017; 139: 18444
5i Wang H, Jui NT. J. Am. Chem. Soc. 2018; 140: 163
5j Vogt DB, Seath CP, Wang H, Jui NT. J. Am. Chem. Soc. 2019; 141: 13203
5k Xu J, Liu J.-W, Wang R, Yang J, Zhao K.-K, Xu H.-J. ACS Catal. 2023; 13: 7339
5l Hendy CM, Pratt CJ, Jui NT, Blakey SB. Org. Lett. 2023; 25: 1397
5m Wright SE, Bandar JS. J. Am. Chem. Soc. 2022; 144: 13032
5n Liu C, Li K, Shang R. ACS Catal. 2022; 12: 4103

Recent reviews on C–F bond transformation of perfluoroalkyl compounds:

6a Xu W, Zhang Q, Shao Q, Xia C, Wu M. Asian J. Org. Chem. 2021; 10: 2454
6b Zhou L. Molecules 2021; 26: 7051
6c Li S, Shu W. Chem. Commun. 2022; 58: 1066
6d Wang Z, Sun Y, Shen L.-Y, Yang W.-C, Meng F, Li P. Org. Chem. Front. 2022; 9: 853
6e Nishimoto Y, Sugihara N, Yasuda M. Synthesis 2022; 54: 2765
6f Yoshida S. Chem. Rec. 2023; 23: e202200308
6g Hooker LV, Bander JS. Angew. Chem. Int. Ed. 2023; 62: e202308880

7 Luo Y.-C, Tong F.-F, Zhang Y, He C.-Y, Zhang X. J. Am. Chem. Soc. 2021; 143: 13971
8 Shreiber ST, Granados BM, Majhi J, Campbell MW, Patel S, Molander GA. Org. Lett. 2022; 24: 8542
9 Sugihara N, Suzuki K, Nishimoto Y, Yasuda M. J. Am. Chem. Soc. 2021; 143: 9308
10 Nacsa ED, MacMillan DW. C. J. Am. Chem. Soc. 2018; 140: 3322

11a Dedeian K, Djurovich PI, Garces FO, Carlson G, Watts RJ. Inorg. Chem. 1991; 30: 1685
11b Tian N, Lenkeit D, Pelz S, Fischer LH, Escudero D, Schiewek R, Klink D, Schmitz OJ, Gonzalez L, Schaferling M, Holder E. Eur. J. Inorg. Chem. 2010; 4875

12a Treat NJ, Sprafke H, Kamer JW, Clark PG, Barton BE, de Alaniz JR, Fors BP, Hawker CJ. J. Am. Chem. Soc. 2014; 136: 16096
12b Discekici EH, Treat NJ, Poelma SO, Mattson KM, Hudson ZM, Luo Y, Hawker CJ, de Alaniz JR. Chem. Commun. 2015; 51: 11705

13 We measured the redox potential of Bu₃SnI (see the Supporting Information). Another possibility is that iodide ion (I^–) functions as a reductant [E(I^•/I^–) = 0.27 V vs SCE]^14a because I^– is often used as a redox mediator in dye-sensitized solar cell technology.^14b

For the redox potential of E(I^•/I^–), see:

14a Bentley CL, Bond AM, Hollenkamp AF, Mahon PJ, Zhang J. J. Phys. Chem. C 2015; 119: 22392

For the function of I^– as a redox mediator, see:

14b Boschloo G, Hagfeldt A. Acc. Chem. Res. 2009; 42: 1819
14c Hagfeldt A, Boschloo G, Sun L, Kloo L, Pettersson H. Chem. Rev. 2010; 110: 6595

15 DFT calculations were conducted using ωB97XD/6-31+G(d,p) for C, H, N, F, and DGDZVP for Sn, I; solvent effect (SMD) = THF.
16 Cockshott ID. Clin. Pharmacokinet. 2004; 43: 855
17 Huang F, Batey RA. Tetrahedron 2007; 63: 7667
18 Thurner A, Faigl F, Ágai B, Tőke L. Synth. Commun. 1998; 28: 443

Supplementary Material

Supporting Information

Photocatalyzed C–F Bond Heteroarylation of Trifluoromethyl­arenes with Heteroarenes: Two Roles of Bu3SnI as Fluoride Ion Scavenger and Activator for Photocatalyst

Photocatalyzed C–F Bond Heteroarylation of Trifluoromethylarenes with Heteroarenes: Two Roles of Bu₃SnI as Fluoride Ion Scavenger and Activator for Photocatalyst