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Synlett 2023; 34(15): 1829-1833
DOI: 10.1055/a-2063-4992
DOI: 10.1055/a-2063-4992
letter
Synthesis of Sulfoximines through Selective Sulfur Alkylation of Sulfinamides Generated In Situ from β-Sulfoximine Esters
The West Light Foundation of the Chinese Academy of Sciences (25E0C30), and the Sichuan Province Science and Technology Support Program (2021ZYD0061).
Abstract
Over the past decade, the incidence of sulfoximine functional groups in pharmaceuticals and agrochemicals has increased significantly. This increase has led to a range of useful strategies for installing a S(VI) functionality into complex organic molecules. Conventional synthetic methods for forming α-substituted sulfonimidoyl motifs rely on late-stage modifications at sulfur and involve multistep routes. We report the development of an efficient and general method for the synthesis of various α-arylated sulfoximines through a selective S-alkylation. This strategy uses economical and readily available β-sulfoximine esters as precursors of sulfinamides and has been demonstrated by the preparation of 31 sulfoximines in good yields (up to 87%).
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2063-4992.
- Supporting Information
Publication History
Received: 17 February 2023
Accepted after revision: 28 March 2023
Accepted Manuscript online:
28 March 2023
Article published online:
11 May 2023
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- 15 Sulfoximines 3; General Procedure The appropriate benzylic bromide 2 (0.12mmol) was added to a solution of TBAB (5 mol%) and β-sulfoximine ester 1 (0.1 mmol) in toluene (1 mL) at 25 °C, and the mixture was stirred at 25 °C for about 8 h until the starting material disappeared (TLC). The solution was then directly purified by column chromatography [silica gel, PE–EtOAc (10:1 to 4:1)]. N-[Benzyl(oxido)phenyl-λ4-sulfanylidene]-2,2-dimethylpropanamide (3a) White solid; yield: 0.026 g (0.082 mmol, 82%); mp 105–107 °C; TLC: Rf = 0.4 (PE–EtOAc, 4:1; UV). 1H NMR (400 MHz, CDCl3): δ = 7.63 (d, J = 7.8 Hz, 3 H), 7.46 (t, J = 7.8 Hz, 2 H), 7.31 (t, J = 7.5 Hz, 1 H), 7.21 (t, J = 7.5 Hz, 2 H), 6.95 (d, J = 7.5 Hz, 2 H), 4.92 (d, J = 13.6 Hz, 1 H), 4.67 (d, J = 13.6 Hz, 1 H), 1.25 (s, 9 H). 13C NMR (101 MHz, CDCl3): δ = 188.8, 135.9, 133.8, 131.3, 129.1, 129.1, 128.6, 128.5, 127.8, 61.9, 41.7, 27.8. HRMS (ESI): m/z [M + Na]+ calcd for C18H21NNaO2S: 338.1185; found: 338.1187.