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Synlett 2005(13): 1965-1983  
DOI: 10.1055/s-2005-872235
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© Georg Thieme Verlag Stuttgart · New York

Hexamethyldisilathiane-Based Thionation of Carbonyl Compounds: A Versatile Approach to Sulfur-Containing Heterocycles

Alessandro Degl’Innocenti*, Antonella Capperucci, Giulio Castagnoli, Irene Malesci
Dipartimento di Chimica Organica, Università di Firenze, via della Lastruccia, 13, 50019 Sesto Fiorentino, Italy
Fax: +39(055)4573585; e-Mail: alessandro.deglinnocenti@unifi.it;
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Publication History

Received 25 April 2005
Publication Date:
20 July 2005 (online)

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Abstract

Reactions of hexamethyldisilathiane (HMDST) with carbonyl compounds under the catalytic activity of CoCl2·6H2O or trimethylsilyltriflate lead to a simple and general access to thioaldehydes and thioketones, which could be isolated as their cycloadducts with dienes. The use of CF3SO3SiMe3 in reactions with cyclohexadiene allows a stereopredetermined access to either the endo- or the exo-isomer. Furthermore, on using β-silyl-substituted acetylenic ketones, a smooth access to acetylenic thioketones can be achieved. In reactions with aromatic and heteroaromatic o-azido aldehydes, the reactivity of HMDST may be finely tuned toward the synthesis of o-azido thioaldehydes, fused isothiazole ring systems, aromatic and heteroaromatic o-amino aldehydes, and o-amino thioaldehydes.

HMDST proved also very efficient in thionating more intriguing substrates such as acylsilanes. Thus, thioacylsilanes, thioformylsilanes, unsaturated thioacylsilanes and -stannanes can be obtained in good yields. Ethylenic thioacylsilanes showed an interesting behavior leading to a general synthesis of functionalized dithiins. Finally, HMDST led also to the synthesis of bis(thioacylsilanes), which led to the formation of new silylated thiaheterocyclic systems.

  • 1 Introduction

  • 2 HMDST-Based Synthesis of Thiocarbonyl Compounds

  • 2.1 Thioaldehydes and Thioketones

  • 2.2 α,β-Unsaturated Thiocarbonyl Compounds

  • 3 Tuning of the Chemical Behavior of Azido Aldehydes

  • 3.1 Azido Thioaldehydes

  • 3.2 Isothiazoles

  • 3.3 Amino Aldehydes

  • 3.4 Amino Thioaldehydes

  • 4 Reactivity of Amino Thioaldehydes

  • 5 Thioacylsilanes and Thioacylstannanes

  • 5.1 Synthesis of Thioacylsilanes and Thioformylsilanes

  • 5.2 α,β-Unsaturated Thioacylsilanes

  • 5.3 α,β-Unsaturated Thioacylstannanes

  • 5.4 Bis(thioacylsilanes)

  • 6 Conclusions

Key words

silyl sulfides - cycloadditions - thiocarbonyl componds - heterocycles - heterodienes

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Capperucci, A.; Degl’Innocenti, A. unpublished results.