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Synlett 2008(14): 2158-2160  
DOI: 10.1055/s-2008-1078027
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Concise Synthesis of Highly Functionalised 4-Thiosugar Derivatives

J. Mike Southern*a, Ian A. O’Neil*b, Peter Kearnsb
a Centre for Synthesis and Chemical Biology and School of Chemistry, University of Dublin, Trinity College, Dublin 2, Ireland
e-Mail: southerj@tcd.ie;
b Robert Robinson Laboratories, Department of Chemistry, University of Liverpool, Crown St, Liverpool L69 7ZD, UK
e-Mail: ion@liv.ac.uk;
Further Information

Publication History

Received 28 May 2008
Publication Date:
05 August 2008 (online)

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Abstract

Cyclisation of a sulfenic acid and an alkene to generate 4-thiosugars has been developed. The first example of the cyclisation of a sulfenic acid and a vinyl chloride is included.

Key words

sulfoxides - cyclisation - epoxides - heterocycles

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13

X-ray Data: 13: C5H10O3S, M = 150.21, T = 213 (2) K, monoclinic, P21, a = 6.0330 (15) Å, b = 7.7668 (13) Å, c = 7.4105 (19) Å, α = 90º, β = 105.65 (3)º, γ = 90º, Z = 2, D calcd = 1.492 Mg/m³, F(000) = 160, absorption coefficient = 0.357 mm-¹, independent reflections 2116/1005 [R(int) = 0.0340] with I ÷ 2σ(I) were used in the analysis; θmax = 24.21˚, final R1 = 0.0254, w R2 = 0.0620. 27: C12H15ClO3S, M = 274.75, T = 213 (2) K, orthorhombic, P212121, a = 8.5497 (17) Å, b = 9.756 (2) Å, c = 15.067 (3) Å, α = 90˚, β = 90˚, γ = 90˚, Z = 4, D calcd = 1.452 Mg/m³, F(000) = 576, absorption coefficient = 0.463 mm-¹, independent reflections 1968 [R(int) = 0.0442] with I ÷ 2σ(I) were used in the analysis; θmax = 24.16˚, final R1 = 0.0400, w R2 = 0.1091. Atomic coordinates and further crystallographic details have been deposited at the Cambridge Crystallographic Data Centre; deposition numbers are CCDC 634841 (13) and CCDC 634842 (27). Copies of these data can be obtained by applying to CCDC, University Chemical Laboratory, Lensfield Road, Cambridge CB2 1EW, UK; fax +44 (1223)336033; email: deposit@ccdc.cam.ac.uk.

14

Preparation of 4-(Benzyloxy)-5-(chloromethyl)-1-oxotetrahydrothiophen-3-ol (27): A solution of vinyl chloride 25 (42 mg, 0.21 mmol) in octane (5 mL) was heated at reflux for 12 h in a nitrogen atmosphere. After cooling the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica gel (5% MeOH in EtOAc) to yield the title compound as a white solid (24 mg, 71%); mp 125-127 ˚C. IR (nujol): 1033 (SO) cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 2.78 [dd, J = 5.0, 15.0 Hz, 1 H, SCHHCH(OH)], 3.28 [m, 1 H, CH(OBn)], 3.41 [dd, J = 2.0, 14.0 Hz, 1 H, CH(OH)], 3.68 (dd, J = 5.0, 11.5 Hz, 2 H, CH2Cl), 4.09 (m, 1 H, SCHCH2Cl), 4.52 [dd, J = 3.5, 10.0 Hz, 1 H, SCHCH(OH)], 4.57 (s, 2 H, OCH 2Ph), 7.27 (m, 5 H, CH2 Ph). ¹³C NMR (100 MHz, CDCl3): δ = 37.9, 58.7, 64.6, 70.2, 74.0, 82.9, 128.5, 129.2, 129.3, 136.8. HRMS (CI, NH3): m/z calcd for C12H16ClO3S: 275.05087; found: 275.05155.