Synlett, Table of Contents Synlett 2023; 34(06): 678-682DOI: 10.1055/a-1921-0875 cluster Chemical Synthesis and Catalysis in India Transition-Metal-Free N-(o-Halo)arylation of Sulfoximines/Sulfonimidamides V. R. Padma Priya , C. P. Irfana Jesin , Ganesh Chandra Nandi ∗ Recommend Article Abstract Buy Article All articles of this category Abstract A transition-metal-free novel route to access N-(o-halo)arylsulfoximines/sulfonimidamides is achieved by the reaction of sulfoximine/sulfonimidamide, aryne precursor, and CCl4/CBr4 in the presence of KF/18-crown-6. The in situ generated benzyne intermediate (from silyl aryl triflate) reacts with the nucleophile (sulfoximine/sulfonimidamide) and halide source (CCl4/CBr4) to yield the product in moderate to good yield. The protocol exhibits broad substrate scope. The regioisomers formed from the unsymmetric aryne precursor were separated effectively via column chromatography. Key words Key wordsaryne precursor - carbon tetrahalide - sulfoximine - sulfonimidamide - transition-metal-free route Full Text References References and Notes 1a Reggelin M, Zur C. Synthesis 2000; 1 1b Ghosh P, Ganguly P, Das S. Asian J. Org. Chem. 2020; 9: 2035 1c Andresini M, Tota A, Degennaro L, Bull JA. Chem. Eur. J. 2021; 27: 17293 2a Lucking U. Angew. Chem. Int. Ed. 2013; 52: 9399 2b Natarajan K, Jesin CP. I, Mercy AA. H, Nandi GC. Org. Biomol. Chem. 2021; 19: 7061 2c Priya VR. P, Natarajan K, Nandi GC. Tetrahedron 2022; 111: 132711 3a Harmata M, Hong X. J. Am. Chem. Soc. 2003; 125: 5754 3b Koep S, Gais HJ, Raabe G. J. Am. Chem. Soc. 2003; 125: 13243 3c Craig D, Grellepois F, White AJ. P. J. Org. Chem. 2005; 70: 6827 4a Bolm C, Martin M, Simic O, Verrucci M. Org. Lett. 2003; 5: 427 4b Moessner C, Bolm C. Angew. Chem. Int. Ed. 2005; 44: 7564 4c Sedelmeier J, Hammerer T, Bolm C. Org. Lett. 2008; 10: 917 5a Bolm C, Moll G, Kahmann JD. Chem. Eur. 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Catal. 2022; 364: 1144 14h Nandi GC, Raju C. Org. Biomol. Chem. 2017; 15: 2234 15 General Procedure for the Synthesis of 4a–n, 5a–d, 7a–f A clean 20 mL Schlenk tube was charged with the corresponding sulfoximine 1 (30 mg, 0.177 mmol, 1.0 equiv.), KF (41 mg, 0.708 mmol, 4.0 equiv.), and 18-crown-6 (187 mg, 0.708 mmol, 4.0 equiv.). Then, anhydrous THF (1 mL), CCl4 (69 μL, 0.709 mmol, 4.0 equiv.), and corresponding benzyne precursor (87 μL, 0.355 mmol, 2.0 equiv.) were added sequentially. The reaction mixture was stirred at 65 °C for 12 h. After completion of the reaction (checked by TLC), the solvent was removed in vacuo, and the product 4 was purified through column chromatography (100–200 mesh SiO2) using 2 - 10% of ethyl acetate in hexane as eluent. CBr4 was used to obtain compound 5. Compound 7 was prepared following the same method using sulfonimidamide 6. Characterization Data for 4a It was obtained as a pale yellow sticky liquid; yield 66% (33 mg obtained from 0.177 mmol of corresponding sulfoximine). 1H NMR (400 MHz, CDCl3): δ = 7.91 (d, J = 8.4 Hz, 2 H), 7.34–7.30 (m, 3 H), 7.18 (dd, J = 8.0, 1.6 Hz, 1 H), 6.97 (td, J = 7.6, 1.6 Hz, 1 H), 6.82 (td, J = 8.0, 1.6 Hz, 1 H), 3.25 (s, 3 H), 2.41 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 144.5, 142.4, 136.1, 130.3, 129.9, 128.7, 128.6, 127.2, 124.0, 122.7, 45.9, 21.7. HRMS (ESI): m/z calcd for C14H14ClNOS [M + H]+: 280.0557; found: 280.0563. Supplementary Material Supplementary Material Supporting Information
