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. 2023 Jan 18;8(4):3812-3820.
doi: 10.1021/acsomega.2c05894. eCollection 2023 Jan 31.

Silver-mediated Room Temperature Reactions for the Synthesis of N-α-Ketoacyl Sulfoximines and N-α,β-Unsaturated Acyl Sulfoximines

Ria Gupta  1   2 , Riyaz Ahmed  1   2 , Zaheen Akhter  1   2 , Mukesh Kumar  1   2 , Parvinder Pal Singh  1
Affiliations

Silver-mediated Room Temperature Reactions for the Synthesis of N-α-Ketoacyl Sulfoximines and N-α,β-Unsaturated Acyl Sulfoximines

Ria Gupta et al. ACS Omega. .

Abstract

Here, we report a silver-mediated coupling of acetylenes with sulfoximines to synthesize N-α-ketoacyl sulfoximines and N-α,β-unsaturated acyl sulfoximines. The reactions are performed under an open atmosphere using the oxidant K2S2O8 and the ligand 2,2-bipyridyl. However, the fate of the product formation is controlled by the type of substrate used. The coupling between aryl acetylenes and sulfoximines afforded the N-α-ketoacylsulfoximines, while the alkyl acetylenes provided the N-α,β-unsaturated acyl sulfoximines. Controlled experiments reveal the differential reactivity patterns of substrates. The labeling 18O experiments showed that water is the source of the incoming oxygen atom for the keto group of N-α-ketoacyl sulfoximines and N-α,β-unsaturated acyl sulfoximines.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Previous and present approaches for the synthesis of N-α-ketoacyl sulfoximines and N-α,β-unsaturated acyl sulfoximines.
Scheme 1
Scheme 1. Coupling of Sulfoximines with Phenyl Acetylene Silver
Reaction conditions: compound 1 (100 mg, 0.429–0.645 mmol), compound 2 (1.5 equiv), K2S2O8 (3 equiv), and 2,2-bipyridyl (2 equiv) in DCM/H2O (3:1, 12 mL solvent), rt, 4–8 h. bIsolated yields.
Scheme 2
Scheme 2. Coupling of Sulfoximines with Alkynylsilver
Reaction conditions: compound 1 (100 mg, 0.429–0.645 mmol), 2 (1.5 equiv), K2S2O8 (3 equiv), and 2,2-bipyridyl (2 equiv) in DCM/H2O (3:1, 12 mL of solvent), rt, 4–8 h. bIsolated yields.
Scheme 3
Scheme 3. Coupling of Sulfoximines with Phenoxylpropynyl Silver
Reaction conditions: compound 1 (100 mg, 0.645 mmol), compound 2 (1.5 equiv 0.967 mmol), K2S2O8 (3 equiv 1.935 mmol), and 2,2-bipyridyl (2 equiv 1.290 mmol), DCM/H2O (3:1, 12 mL), rt, 5 h. bIsolated yields.
Scheme 4
Scheme 4. Coupling of Sulfoximines with In-Situ-Generated Phenyl Acetylene Silver
Reaction condition: compound 1 (100 mg, 0.645 mmol), AgNO3 (0.5 equiv, 0.322 mmol), K2S2O8 (3 equiv, 1.935 mmol), and 2,2-bipyridyl (2 equiv, 1.290 mmol), DCM/H2O (3:1, 12 mL), rt, 7 h.
Scheme 5
Scheme 5. Controlled Experiments
Figure 2
Figure 2
Labeling experiment (a) LC–MS chromatogram of the reaction mixture with DCM and normal water; (b) MS of the reaction mixture for 3a; (c) expanded MS of 3a; (d) LC–MS chromatogram of the reaction mixture with DCM and 18O labeled H2O; (e) MS of 18O labeled 3a; (f) expanded MS of 18O labeled 3a.
Figure 3
Figure 3
Plausible reaction mechanism for the formation of N-α-ketoacyl sulfoximines and N-α,β-unsaturated acyl sulfoximines.
See this image and copyright information in PMC

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