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Synlett 2008(1): 108-110  
DOI: 10.1055/s-2007-1000838
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Facile Synthesis of 1-Arenesulfonylazetidines through Reaction of 1-Arenesulfonylaziridines with Dimethylsulfoxonium Methylide Generated under Microwave Irradiation

Sarika Malik*, Upender K. Nadir
Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110 016, India
Fax: +91(11)26582037; e-Mail: sarika.malik@mail2.iitd.ac.in;
Further Information

Publication History

Received 28 July 2007
Publication Date:
11 December 2007 (online)

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Abstract

A simple, efficient and general method has been developed for the synthesis of 1-arenesulfonylazetidines through a one-pot reaction of 1-arenesulfonylaziridines with dimethylsulfoxonium methylide, generated under microwave irradiation, using alumina as solid support.

Key words

azo compounds - ring expansion - sulfur - ylides - heterocycles

    References and Notes

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33

General Method for the Synthesis of 1-Arenesulfonyl-azetidines: The pertinent aziridine (1 mmol), trimethylsulfoxonium iodide (3 mmol) and KOH (3 mmol) were loaded on neutral alumina (0.5 mmol) solid support. This mixture was irradiated with microwaves for the specified time (Table [1] ). Only a single product (as shown by TLC) was formed. The reaction was quenched by addition of cold H2O. The product was extracted with EtOAc and purified by simple crystallization or through column chromatography on silica gel.cis -2-Methyl-3-phenyl-1-(4-toluenesulfonyl)azetidine (3f): white crystalline solid; mp 105-106 °C; yield: 79%. IR: 1333, 1164 (SO2) cm-1. 1H NMR (300 MHz, CDCl3): δ = 7.65 (m, 5 H), 7.32 (s, 4 H), 4.26 (q, J = 7 Hz, 1 H), 3.93 (distorted d, J = 6 Hz, 2 H), 3.41 (m, 1 H), 2.39 (s, 3 H), 0.98 (d, J = 7 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 127.2-137.4 (ArC), 63.02 (d), 53.47 (t), 38.17 (d), 21.42 (q), 17.02 (q). Anal. Calcd for C17H19NSO2: C, 67.77; H, 6.31; N, 4.65. Found: C, 67.10; H, 6.40; N, 4.51. MS (FAB): m/z = 302 [MH+].2-Hexyl-1-(4-toluenesulfonyl)azetidine (3g): viscous oil; yield: 79%. IR: 1333, 1164 (SO2) cm-1. 1H NMR (300 MHz, CDCl3): δ = 7.65 (d, 2 H), 7.32 (d, 2 H), 3.42-3.77 (complex m, 3 H), 2.38 (s, 3 H), 1.84 (complex m, 2 H), 1.18-1.32 (m, 10 H, aliphatic), 0.81 (t, J = 7 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 128.26-143.80 (ArC), 66.35 (d), 47.50 (t), 36.02 (t), 31.70 (t), 29.66 (t), 28.59 (t), 24.13 (t), 22.66 (t), 21.42 (q), 14.09 (q). Anal. Calcd for C16H25NSO2: C, 65.08; H, 8.47; N, 4.74. Found: C, 64.88; H, 7.80; N, 4.30. MS (FAB): m/z = 296 [MH+]. 2-(4-Chlorophenyl)-1-(4-toluenesulfonyl)azetidine (3h): white crystalline solid; mp 108-109.5 °C; yield: 72%. IR: 1333, 1160 (SO2) cm-1. 1H NMR (300 MHz, CDCl3): δ = 7.51 (m, 4 H), 7.31 (s, 4 H), 4.89 (t, J = 8 Hz, 1 H), 3.77 (dd, J = 6, 8 Hz, 2 H), 2.40 (s, 3 H), 2.25 (m, J = 8 Hz, 2 H). 13C NMR (75 MHz, CDCl3): δ = 127.83-139.14 (ArC), 65.11 (d), 47.43 (t), 25.89 (t), 21.41 (q). Anal. Calcd for C16H16NSO2Cl: C, 59.72; H, 4.97; N, 4.35. Found: C, 59.72; H, 5.08; N, 4.07. MS (FAB): m/z = 322 [M+].2-(4-Bromophenyl)-1-(4-toluenesulfonyl)azetidine (3i): white crystalline solid; mp 118-119 °C; yield: 71%. IR: 1330, 1164 (SO2) cm-1. 1H NMR (300 MHz, CDCl3): δ = 7.51 (m, 4 H), 7.28 (s, 4 H), 4.78 (t, J = 8 Hz, 1 H), 3.78 (dd, J = 6, 8 Hz, 2 H), 2.38 (s, 3 H), 2.25 (m, J = 8 Hz, 2 H). 13C NMR (75 MHz, CDCl3): δ = 127.83-139.14 (ArC), 65.15 (d), 47.43 (t), 25.89 (t), 21.42 (q). Anal. Calcd for C16H16NSO2Br: C, 52.45; H, 4.37; N, 3.82. Found: C, 52.22; H, 4.44; N, 3.14. MS (FAB): m/z = 366 [M+].2-(4-Methylphenyl)-1-(4-toluenesulfonyl)azetidine (3j): white crystalline solid; mp 110-111 °C; yield: 71%. IR: 1334, 1163 (SO2) cm-1. 1H NMR (300 MHz, CDCl3): δ = 7.42 (m, 4 H), 7.02 (m, 4 H), 4.87 (t, J = 8 Hz, 1 H), 3.77 (dd, J = 6, 8 Hz, 2 H), 2.40 (s, 3 H), 2.33 (s, 3 H), 2.28 (m, 2 H). 13C NMR (75 MHz, CDCl3): δ = 123.3-140.29 (ArC), 65.83 (d), 47.27 (t), 25.83 (t), 21.4 (q), 21.38 (q). Anal. Calcd for C17H19NSO2: C, 67.77; H, 6.31; N, 4.65. Found: C, 67.11; H, 5.95; N, 3.96. MS (FAB): m/z = 302 [MH+].

34

The reaction vials were placed in the MW reactor supplied with a safety valve for release of overpressure.

35

After the set temperature of 90 °C is reached, the power regulates itself to maintain the reaction temperature.