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

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

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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

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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.

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