An Efficient Protecting-Group-Free Synthesis of Vinylic Sulfoximines via Horner–Wadsworth–Emmons Reaction

Praveen K. Chinthakindi; Ganesh Chandra Nandi; Thavendran Govender; Hendrik G. Kruger; Tricia Naicker; Per I. Arvidsson

doi:10.1055/s-0035-1561573

Synlett, Table of Contents

Synlett 2016; 27(09): 1423-1427
DOI: 10.1055/s-0035-1561573

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An Efficient Protecting-Group-Free Synthesis of Vinylic Sulfoximines via Horner–Wadsworth–Emmons Reaction

Praveen K. Chinthakindi

^aCatalysis and Peptide Research Unit, University of KwaZulu-Natal, Durban 4000, South Africa, Email: Naickert1@ukzn.ac.za

,

Ganesh Chandra Nandi

^aCatalysis and Peptide Research Unit, University of KwaZulu-Natal, Durban 4000, South Africa, Email: Naickert1@ukzn.ac.za

^cOrganic Chemistry Section, CSIR-National Institute for Interdisciplinary Science and Technology, Trivandrum 695019, India

,

Thavendran Govender

^aCatalysis and Peptide Research Unit, University of KwaZulu-Natal, Durban 4000, South Africa, Email: Naickert1@ukzn.ac.za

,

Hendrik G. Kruger

^aCatalysis and Peptide Research Unit, University of KwaZulu-Natal, Durban 4000, South Africa, Email: Naickert1@ukzn.ac.za

,

Tricia Naicker*

^aCatalysis and Peptide Research Unit, University of KwaZulu-Natal, Durban 4000, South Africa, Email: Naickert1@ukzn.ac.za

,

Per I. Arvidsson*

^aCatalysis and Peptide Research Unit, University of KwaZulu-Natal, Durban 4000, South Africa, Email: Naickert1@ukzn.ac.za

^bScience for Life Laboratory, Drug Discovery & Development Platform & Division of Translational Medicine and Chemical Biology, Department of Medical Biochemistry and Biophysics, Karolinska Institutet, S-171 21 Solna, Sweden Email: per.arvidsson@scilifelab.se

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Abstract

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Abstract

Herein, we report a convenient synthesis of aryl-substituted (E)-vinylic NH-sulfoximines via the Horner–Wadsworth–Emmons reaction without the use of protection–deprotection group strategies.

Key words

phosphonate - Horner–Wadsworth–Emmons - vinylic sulfoximine

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References

References and Notes
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17 General Procedure for the Synthesis of Compounds 7a–f and 8a,b n-BuLi (1.2 equiv of 1.6 M solution in hexane) was added to a solution of diethylphenylsulfonimidoylmethylphosphonate (1.0 equiv) in dry THF (4 mL) kept at –78 °C. The reaction was stirred for 1 h before sequential addition of aldehyde (1.3 equiv). Then the resulting reaction mixture was stirred at –78 °C for 1 h. After completion, the reaction mixture was neutralized with NH₄Cl and extracted with EtOAc (3 × 20 mL) to give the title product. (E)-[2-(Phenylsulfonimidoyl)vinyl]benzene (7a) ¹HNMR (400 MHz, CDCl₃): δ = 8.03–8.01 (2 H, m, ArH), 7.63 (1 H, d, J = 15.2 Hz), 7.58–7.48 (3 H, m, ArH), 7.46–7.44 (2 H, m, ArH), 7.36–7.33 (3 H, m, ArH), 6.96 [1 H, d, J = 15.2 Hz, (E)-CH=CH]. ¹³C NMR (100 MHz, CDCl₃): δ = 142.8, 141.7, 132.8, 132.6, 130.9, 130.0, 129.4, 129.3, 129.0, 128.5, 128.3 (2), 127.9 (2). IR (ATR): ν = 3262, 3059, 1703, 1614, 1575, 1215, 1070, 744, 709, 607 cm^–1. HRMS (ESI⁺): m/z [M + H]⁺ calcd for C₁₄H₁₃NOSH⁺: 244.0791; found: 244.0811 [M + H]⁺.
18 General Procedure for the Synthesis of Compound 7g n-BuLi (1.2 equiv of 1.6 M solution in hexane) was added to a solution of diethylphenylsulfonimidoylmethylphosphonate (1.0 equiv) in dry THF (4 mL) kept at –78 °C. The reaction was stirred for 1 h before sequential addition of acetophenone (1.3 equiv). Then the resulting reaction mixture was stirred at r.t. for 1 h. The reaction mixture was then neutralized with aq NH₄Cl and extracted with EtOAc (3 × 20 mL) to give the title product after workup. (E)-(2-Phenylprop-1-enylsulfonimidoyl)benzene (7g) ¹H NMR (400 MHz, CDCl₃): δ = 8.06–8.04 (2 H, m, ArH), 7.63–7.53 (4 H, m, ArH), 7.44–7.42 (2 H, m, ArH), 7.38–7.33 (2 H, m, ArH), 6.89 (1 H, s, CH=C), 2.44 (3H , d, J = 1 Hz, CH=CCH ₃). ¹³C NMR (100 MHz, CDCl₃): δ = 139.9, 133.4, 130.2, 129.5 (3 C), 128.9 (3 C), 128.0 (3 C), 126.5 (2 C), 16.9. IR (ATR): ν = 2958, 2920, 2849, 2171, 2018, 1456, 1123, 1049, 623, 499 cm^–1. HRMS (ESI⁺): m/z [M + H]⁺ calcd for for C₁₅H₁₅NOSH⁺: 258.0947; found: 258.0967 [M + H]⁺.
19 Senthil Kumar P, Bharatam PV. Tetrahedron 2005; 61: 5633

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