Visible-Light-Induced Hydrogen-Atom-Transfer Catalysis for the Regioselective Hydroacylation of N-Sulfonylimine Esters with Aldehydes

Zhiyong Chi; Siyuan Huang; Guo Tang; Qianyi Zhao; Lei Gong

doi:10.1055/a-2550-1878

Synlett, Table of Contents

Synlett 2025; 36(11): 1553-1558
DOI: 10.1055/a-2550-1878

letter

Hydrogen Atom Transfer Reactions

Visible-Light-Induced Hydrogen-Atom-Transfer Catalysis for the Regioselective Hydroacylation of N-Sulfonylimine Esters with Aldehydes

Authors

Zhiyong Chi‡

^aKey Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, P. R. of China
Siyuan Huang‡

^aKey Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, P. R. of China
Guo Tang

^aKey Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, P. R. of China

^bState Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources, College of Chemistry, Xinjiang University, Urumqi 830017 Xinjiang, P. R. of China
Qianyi Zhao

^cSchool of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, P. R. of China
Lei Gong

^aKey Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, P. R. of China

Abstract

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Abstract

The hydroacylation of unsaturated π-systems with aldehydes offers a direct and atom-economical route for introducing both a hydrogen atom and an acyl group into an organic molecule. Whereas hydroacylation reactions with alkanes and alkenes are well established, transformations involving imines have been much less successful. Existing approaches often favor C–C bond formation over C–N bond formation, due to the inherent properties of imines and acyl radicals. We present a photochemical approach that specifically targets N-sulfonylimine esters in combination with aldehydes. This reaction is facilitated by a decatungstate-salt-mediated double hydrogen-atom-transfer (HAT) activation that uniquely promotes the formation of C–N bonds under mild and simple conditions. Our method permits the efficient synthesis of a broad spectrum of distinctive N-sulfonyl N-carbonyl amide products with exclusive regioselectivity. We expect this streamlined method to expand the synthetic toolkit available for constructing complex nitrogen-containing compounds.

Key words

visible light - photocatalysis - hydrogen atom transfer - hydroacylation - imines - regioselectivity

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References

References and Notes

1a Ghosh A, Johnson KF, Vickerman KL, Walker JA, Stanley LM. Org. Chem. Front. 2016; 3: 639
1b Whyte A, Bajohr J, Torelli A, Lautens M. Angew. Chem. Int. Ed. 2020; 59: 16409
1c Jhuang H.-S, Reddy DM, Chen T.-H, Lee C.-F. Asian J. Org. Chem. 2016; 5: 1452

2a Chen Q.-A, Kim DK, Dong VM. J. Am. Chem. Soc. 2014; 136: 3772
2b Jun C.-H, Lee D.-Y, Lee H, Hong J.-B. Angew. Chem. Int. Ed. 2000; 39: 3070
2c Wu J, Gao W.-X, Huang X.-B, Zhou Y.-B, Liu M.-C, Wu H.-Y. Org. Chem. Front. 2021; 8: 6048
2d Leung JC, Krische MJ. Chem. Sci. 2012; 3: 2202

3a von Delius M, Le CM, Dong VM. J. Am. Chem. Soc. 2012; 134: 15022
3b Coxon TJ, Fernández M, Barwick-Silk J, McKay AI, Britton LE, Weller AS, Willis MC. J. Am. Chem. Soc. 2017; 139: 10142
3c Zhang H.-J, Bolm C. Org. Lett. 2011; 13: 3900
3d Murphy SK, Bruch A, Dong VM. Chem. Sci. 2015; 6: 174

4a Liu H, Xue F, Wang M, Tang X, Wu J. Synlett 2020; 32: 406
4b Voutyritsa E, Kokotos CG. Angew. Chem. Int. Ed. 2020; 59: 1735
4c Biswas S, Chandu P, Garai S, Sureshkumar D. Org. Lett. 2023; 25: 7863
4d Zhang M, Ruzi R, Xi J, Li N, Wu Z, Li W, Yu S, Zhu C. Org. Lett. 2017; 19: 3430
4e Fan P, Zhang C, Lan Y, Lin Z, Zhang L, Wang C. Chem. Commun. 2019; 55: 12691
4f Zhao X, Li B, Xia W. Org. Lett. 2020; 22: 1056
4g Zheng L, Xia P.-J, Zhao Q.-L, Qian Y.-E, Jiang W.-N, Xiang H.-Y, Yang H. J. Org. Chem. 2020; 85: 11989
4h Zhang L, Chen S, He H, Li W, Zhu C, Xie J. Chem. Commun. 2021; 57: 9064
4i Pálvölgyi ÁM, Ehrschwendtner F, Schnürch M, Bica-Schröder K. Org. Biomol. Chem. 2022; 20: 7245
4j Tao X, Wang Q, Kong L, Ni S, Pan Y, Wang Y. ACS Catal. 2022; 12: 15241
4k Saga Y, Nakayama Y, Watanabe T, Kondo M, Masaoka S. Org. Lett. 2023; 25: 1136
4l Takekawa Y, Nakagawa M, Nagao K, Ohmiya H. Chem. Eur. J. 2023; 29: e202301484

5a Murugesan V, Muralidharan A, Anantharaj GV, Chinnusamy T, Rasappan R. Org. Lett. 2022; 24: 8435
5b Yang J, Song M, Zhou H, Wang G, Ma B, Qi Y, Huo C. Org. Lett. 2020; 22: 8407

6a Koutoulogenis GS, Kokotou MG, Voutyritsa E, Limnios D, Kokotos CG. Org. Lett. 2017; 19: 1760
6b Stini NA, Poursaitidis ET, Nikitas NF, Kartsinis M, Spiliopoulou N, Ananida-Dasenaki P, Kokotos CG. Org. Biomol. Chem. 2023; 21: 1284
6c Liu L, Wang J, Feng X, Xu K, Liu W, Peng X, Du H, Tan J. Chin. J. Chem. 2024; 42: 1230
6d Li Q, Chen J, Luo Y, Xia Y. Org. Lett. 2024; 26: 1517

7 Mistry P, Das S, Patra R, Chatterjee I. Org. Chem. Front. 2024; 11: 6778
8 Zhang H.-H, Yu S. Org. Lett. 2019; 21: 3711
9 Zhong Z, Wu H, Chen X, Luo Y, Yang L, Feng X, Liu X. J. Am. Chem. Soc. 2024; 146: 20401
10 Liu M.-S, Shu W. ACS Catal. 2020; 10: 12960

11a Li Y, Lei M, Gong L. Nat. Catal. 2019; 2: 1016
11b Chi Z, Liao J.-B, Cheng X, Ye Z, Yuan W, Lin Y.-M, Gong L. J. Am. Chem. Soc. 2024; 146: 10857
11c Yang F, Chi L, Ye Z, Gong L. J. Am. Chem. Soc. 2025; 147: 1767
11d Li Q.-Y, Cheng S, Ye Z, Huang T, Yang F, Lin Y.-M, Gong L. Nat. Commun. 2023; 14: 6366
11e Huang T, Du P, Cheng X, Lin Y.-M. J. Am. Chem. Soc. 2024; 146: 24515
11f Huang H, Jiang Y, Yuan W, Lin Y.-M. Angew. Chem. Int. Ed. 2024; 63: e202409653
11g Ye Z, Yu Y, Lin Y.-M, Chen Y, Song S, Gong L. Nat. Synth. 2023; 2: 766
11h Gong L. Nat. Synth. 2022; 1: 915

12a Liu Z, D’Amico F, Martin R. J. Am. Chem. Soc. 2024; 146: 28624
12b Chen J, Tan C, Rodrigalvarez J, Zhang S, Martin R. Angew. Chem. Int. Ed. 2024; 63: e202406485
12c Zhou W, Dmitriev IA, Melchiorre P. J. Am. Chem. Soc. 2023; 145: 25098
12d Finis DS, Nicewicz DA. J. Am. Chem. Soc. 2024; 146: 16830
12e Schlegel M, Qian S, Nicewicz DA. ACS Catal. 2022; 12: 10499
12f Xu Z, Fu L, Fang X, Huang B, Zhou L, Wan J.-P. Org. Lett. 2021; 23: 5049
12g Yan X, Pang Y, Zhou Y, Chang R, Ye J. J. Am. Chem. Soc. 2025; 147: 1186
12h Kikuchi T, Yamada K, Yasui T, Yamamoto Y. Org. Lett. 2021; 23: 4710
12i Xie H, Breit B. Org. Lett. 2024; 26: 4438

13 CCDC 2412678 contains the supplementary crystallographic data for compound 33. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
14 Buettner GR. Free Radical Biol. Med. 1987; 3: 259
15 Dong J, Wang X, Wang Z, Song H, Liu Y, Wang Q. Chem. Sci. 2020; 11: 1026
16 Ethyl 2-Benzoyl-2,3-dihydro-1,2-benzisothiazole-3-carboxylate 1,1-Dioxide (3); Typical Procedure A dried Schlenk tube (10 mL) was charged with the N-sulfonylimine ester 1a (23.9 mg, 0.10 mmol), PhCHO (2a; 21.2 mg, 0.20 mmol), TBADT (6.6 mg, 0.0020 mmol), Na₂CO₃ (10.6 mg, 0.10 mmol), and MeCN (1.0 mL). The mixture was then degassed with argon through three freeze–pump–thaw cycles. The Schlenk tube was positioned approximately 4 cm from a 50 W lamp, and the mixture was stirred at 25 °C for 24 h. The resulting mixture was then purified by flash column chromatography [silica gel, PE–EtOAc (4:1)] to give a white solid; yield: 30.0 mg (0.087 mmol, 87%). ¹H NMR (400 MHz, CDCl₃): δ = 7.84 (d, J = 8.1 Hz, 2 H), 7.78–7.63 (m, 3 H), 7.56 (q, J = 7.5 Hz, 2 H), 7.45 (t, J = 7.6 Hz, 2 H), 6.13 (s, 1 H), 4.32–4.14 (m, 2 H), 1.25 (t, J = 7.1 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 168.32, 166.39, 134.32, 134.20, 133.59, 132.57, 130.76, 128.71, 128.41, 128.36, 125.38, 62.96, 59.86, 14.04. HRMS (ESI-TOF): m/z [M + Na]⁺ calcd for C₁₇H₁₅NNaO₅S: 368.0563; found: 368.0567.

Supplementary Material