Desulfonylative Radical Truce–Smiles Rearrangement Utilizing the Benzimidazoline and Benzimidazolium Redox Couple

Ryo Miyajima; Manon Okamura; Kazuki Oomori; Hajime Iwamoto; Kan Wakamatsu; Eietsu Hasegawa

doi:10.1055/a-2153-6594

Synlett, Table of Contents

Synlett 2024; 35(03): 352-356
DOI: 10.1055/a-2153-6594

cluster

Organic Chemistry Under Visible Light: Photolytic and Photocatalytic Organic Transformations

Desulfonylative Radical Truce–Smiles Rearrangement Utilizing the Benzimidazoline and Benzimidazolium Redox Couple

Authors

Ryo Miyajima

^aDepartment of Chemistry, Faculty of Science, Niigata University, 8050 Ikarashi-2, Nishi-ku, Niigata 950-2181, Japan
Manon Okamura

^aDepartment of Chemistry, Faculty of Science, Niigata University, 8050 Ikarashi-2, Nishi-ku, Niigata 950-2181, Japan
Kazuki Oomori

^aDepartment of Chemistry, Faculty of Science, Niigata University, 8050 Ikarashi-2, Nishi-ku, Niigata 950-2181, Japan
Hajime Iwamoto

^aDepartment of Chemistry, Faculty of Science, Niigata University, 8050 Ikarashi-2, Nishi-ku, Niigata 950-2181, Japan
Kan Wakamatsu

^bDepartment of Chemistry, Faculty of Science, Okayama University of Science, 1-1 Ridai-cho, Kita-ku, Okayama 700-0005, Japan
Eietsu Hasegawa∗

^aDepartment of Chemistry, Faculty of Science, Niigata University, 8050 Ikarashi-2, Nishi-ku, Niigata 950-2181, Japan

Abstract

All articles of this category

This letter is dedicated to Professor Dennis P. Curran (University of Pittsburgh), who is a distinguished chemist for synthetic application of free radical chemistry, on the occasion of his Koki anniversary (70^th birthday).

Abstract

We have developed protocols for promoting redox reactions utilizing the 2-substituted 1,3-dimethylbenzimidazoline (BIH–R) and benzimidazolium (BI⁺–R) couples which were applied to the desulfonylative radical Truce–Smiles rearrangement. Expected rearrangement products formed in modest to good yields in these processes, in which added or in situ generated BIH–R serve as electron- and hydrogen-atom-donating reagents or photocatalysts. DFT calculations were carried out to gain the information about the radical intermediates involved in the rearrangement reaction.

Key words

benzimidazoline and benzimidazolium redox couple - single-electron transfer - photoreducing catalyst - radical Truce–Smiles rearrangement - desulfonylative aryl migration

Full Text

References

References and Notes

1a Eberson L. Electron Transfer Reactions in Organic Chemistry. Springer; Berlin: 1987
1b Photoinduced Electron Transfer, Parts A–D. Fox MA, Chanon M. Elsevier; Amsterdam: 1988
1c Advances in Electron Transfer Chemistry, Vol. 1–6. Mariano PS. JAI; Greenwich: 1991
1d Kavarnos GJ. Fundamental of Photoinduced Electron Transfer. VCH; New York: 1993
1e Connelly NG, Geiger WE. Chem. Rev. 1996; 96: 877
1f Electron Transfer in Chemistry, Vol. 1–5. Balzani V. Wiley-VCH; Weinheim: 2001
1g Organic Electrochemistry, 4th ed. Lund H, Hammerich O. Marcel Dekker; New York: 2001
1h Fukuzumi S. Electron Transfer: Mechanisms and Applications . Wiley-VCH; Weinheim: 2020

2a Schmittel M, Burghart A. Angew. Chem., Int. Ed. Engl. 1997; 36: 2550
2b Berger DJ, Tanko JM. The Chemistry of Double-Bonded Functional Groups . Patai S. Wiley; New York: 1997: 1281
2c Roth HD. Reactive Intermediate Chemistry . Moss RA, Platz MS, Jones MJr. Wiley; Hoboken: 2004: 205
2d Todres ZV. Ion-Radical Organic Chemistry Principles and Applications, 2nd ed. CRC Press; Boca Raton: 2009
2e Zhang N, Samanta SR, Rosen BM, Percec V. Chem. Rev. 2014; 114: 5848
2f Studer A, Curran DP. Nat. Chem. 2014; 6: 765
2g Lee KN, Ngai M.-Y. Chem. Commun. 2017; 53: 13093
2h Syroeshkin MA, Kuriakose F, Saverina EA, Timofeeva VA, Egorov MP, Alabugin IV. Angew. Chem. Int. Ed. 2019; 58: 5532
2i Peter A, Agasti S, Knowles O, Pye E, Procter DJ. Chem. Soc. Rev. 2021; 50: 5349

3 Zhu X.-Q, Zhang M.-T, Yu A, Wang C.-H, Cheng J.-P. J. Am. Chem. Soc. 2008; 130: 2501

4a Chikashita H, Itoh K. Bull. Chem. Soc. Jpn. 1986; 59: 1747
4b Ramos SM, Tarazi M, Wuest JD. J. Org. Chem. 1987; 52: 5437
4c Chen J, Tanner DD. J. Org. Chem. 1988; 53: 3897
4d Hasegawa E, Kato T, Kitazume T, Yanagi K, Hasegawa K, Horaguchi T. Tetrahedron Lett. 1996; 37: 7079
4e Lee I.-SH, Jeoung EH, Kreevoy MM. J. Am. Chem. Soc. 1997; 119: 2722
4f Schwarz DE, Cameron TM, Hay PJ, Scott BL, Tumas W, Thorn DL. Chem. Commun. 2005; 5919
4g Wei P, Oh JH, Dong G, Bao Z. J. Am. Chem. Soc. 2010; 132: 8852
4h Tamaki Y, Koike K, Morimoto T, Ishitani O. J. Catal. 2013; 304: 22
4i Horn M, Schappele LH, Lang-Wittkowski G, Mayr H, Ofial AR. Chem. Eur. J. 2013; 19: 249
4j Kim SS, Bae S, Jo WH. Chem. Commun. 2015; 51: 17413
4k Hasegawa E, Takizawa S. Aust. J. Chem. 2015; 68: 1640
4l Zhang Y, Petersen JL, Milsmann CA. J. Am. Chem. Soc. 2016; 138: 13115
4m Mehrotra S, Raje S, Jain AK, Angamuthu R. ACS Sustainable Chem. Eng. 2017; 5: 6322
4n Iakovenko R, Hlaváč J. Green Chem. 2021; 23: 440
4o Tun SL, Mariappan SV. S, Pigge FC. J. Org. Chem. 2022; 87: 8059
4p Wang Y.-F, Zhang M.-T. J. Am. Chem. Soc. 2022; 144: 12459

5a Ilic S, Alherz A, Musgrave CB, Glusac KD. Chem. Commun. 2019; 55: 5583
5b Rohrbach S, Shah RS, Tuttle T, Murphy JA. Angew. Chem. Int. Ed. 2019; 58: 11454
5c Kodama T, Kubo M, Shinji W, Ohkubo K, Tobisu M. Chem. Sci. 2020; 11: 12109
5d Weerasooriya RB, Drummer MC, Phelan BT, Gesiorski JL, Sprague-Klein EA, Chen LX, Glusac KD. J. Phys. Chem. C 2022; 126: 17816
5e Xie W, Xu J, Md Idros U, Katsuhira J, Fuki M, Hayashi M, Yamanaka M, Kobori Y, Matsubara R. Nat. Chem. 2023; 15: 794

6a Hasegawa E, Ohta T, Tsuji S, Mori K, Uchida K, Miura T, Ikoma T, Tayama E, Iwamoto H, Takizawa S, Murata S. Tetrahedron 2015; 71: 5494
6b Hasegawa E, Nagakura Y, Izumiya N, Matsumoto K, Tanaka T, Miura T, Ikoma T, Iwamoto H, Wakamatsu K. J. Org. Chem. 2018; 83: 10813
6c Hasegawa E, Nakamura S, Oomori K, Tanaka T, Iwamoto H, Wakamatsu K. J. Org. Chem. 2021; 86: 2556

7a Hasegawa E, Izumiya N, Miura T, Ikoma T, Iwamoto H, Takizawa S, Murata S. J. Org. Chem. 2018; 83: 3921
7b Hasegawa E, Tanaka T, Izumiya N, Kiuchi T, Ooe Y, Iwamoto H, Takizawa S, Murata S. J. Org. Chem. 2020; 85: 4344
7c Tanaka T, Kiuchi T, Ooe Y, Iwamoto H, Takizawa S, Murata S, Hasegawa E. ACS Omega 2022; 7: 4655

8 Miyajima R, Ooe Y, Miura T, Ikoma T, Iwamoto H, Takizawa S, Hasegawa E. J. Am. Chem. Soc. 2023; 145: 10236
9 Miyajima R, Kiuchi T, Ooe Y, Iwamoto H, Takizawa S, Hasegawa E. J. Photochem. Photobiol. 2023; 16: 100195

10a Henderson AR. P, Kosowan JR, Wood TE. Can. J. Chem. 2017; 95: 483
10b Holden CM, Greaney MF. Chem. Eur. J. 2017; 23: 8992

11a Huynh M, De Abreu M, Belmont P, Brachet E. Chem. Eur. J. 2021; 27: 3581
11b Allen AR, Noten EA, Stephenson CR. J. Chem. Rev. 2022; 122: 2695

12 Li Y, Hu B, Dong W, Xie X, Wan J, Zhang Z. J. Org. Chem. 2016; 81: 7036
13 Hasegawa E, Yoshioka N, Tanaka T, Nakaminato T, Oomori K, Ikoma T, Iwamoto H, Wakamatsu K. ACS Omega 2020; 5: 7651
14 Typical Reaction Procedures (a) Reaction of 2b Utilizing 1e-H (Scheme [4]) A solution of 2b (41.7 mg, 0.10 mmol), 1e-H (58.7 mg, 0.15 mmol), and AcOH (11.5 μL, 0.20 mmol) in N₂ pre-purged DMF (2.0 mL) was stirred at room temperature for 1 h. The reaction mixture was worked-up in the manner described in the Supporting Information. No recovery of 2b (conv. 100%) and the yield of 3b (0.070 mmol, 70%) were determined by ¹H NMR spectroscopy (Figure S6).(b) Photocatalytic Reaction of 2d Utilizing 1f·ClO₄(Scheme [6]) An N₂ pre-purged solution of 2d (41.5 mg, 0.10 mmol), 1f·ClO₄ (13.0 mg, 0.02 mmol), pic-BH₃ (15.1 mg, 0.12 mmol), and AcOH (28.6 μL, 0.50 mmol) in DMF (2.0 mL) was irradiated with Xe lamp at room temperature for 1 h. The photolysate was worked-up in the manner described in the Supporting Information. No recovery of 2d (conv. 100%) and the yield of 3d (0.060 mmol, 60%) were determined by ¹H NMR spectroscopy (Figure S14).
15 Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Petersson GA, Nakatsuji H, Li X, Caricato M, Marenich AV, Bloino J, Janesko BG, Gomperts R, Mennucci B, Hratchian HP, Ortiz JV, Izmaylov AF, Sonnenberg JL, Williams-Young D, Ding F, Lipparini F, Egidi F, Goings J, Peng B, Petrone A, Henderson T, Ranasinghe D, Zakrzewski VG, Gao J, Rega N, Zheng G, Liang W, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Throssell K, Montgomery JA. Jr, Peralta JE, Ogliaro F, Bearpark MJ, Heyd JJ, Brothers EN, Kudin KN, Staroverov VN, Keith TA, Kobayashi R, Normand J, Raghavachari K, Rendell AP, Burant JC, Iyengar SS, Tomasi J, Cossi M, Millam JM, Klene M, Adamo C, Cammi R, Ochterski JW, Martin RL, Morokuma K, Farkas O, Foresman JB, Fox DJ. Gaussian 16, Revision C.01. Gaussian, Inc; Wallingford CT (USA): 2016

16a Anderse ML, Mathivanan N, Wayner DD. M. J. Am. Chem. Soc. 1996; 118: 4871
16b Andrieux CP, Savéant J.-M, Tallec A, Tardivel R, Tardy C. J. Am. Chem. Soc. 1996; 118: 9788
16c Andrieux CP, Savéant J.-M, Tallec A, Tardivel R, Tardy C. J. Am. Chem. Soc. 1997; 119: 2420
16d Anderse ML, Long W, Wayner DD. M. J. Am. Chem. Soc. 1997; 119: 6590

Supplementary Material

Supporting Information (PDF) (opens in new window)