Abstract: Reactions of hexamethyldisilathiane (HMDST) with carbonyl compounds under the catalytic activity of CoCl2.6H2O or trimethylsilyltriflate leads to a simple and general access to thioal-dehydes 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 -silyl substi-tuted 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, thioformylsi-lanes, unsaturated thioacylsilanes and –stannanes can be obtained in good yields. Ethylenic thioacylsilanes showed an interesting behaviour 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
“Hexamethyldisilathiane based thionation of carbonyl compounds: a versatile approach to sulfur containing heterocycles” / A. DEGL'INNOCENTI; A. CAPPERUCCI; G. CASTAGNOLI; I. MALESCI. - In: SYNLETT. - ISSN 0936-5214. - STAMPA. - .:(2005), pp. 1965-1983.
“Hexamethyldisilathiane based thionation of carbonyl compounds: a versatile approach to sulfur containing heterocycles”
DEGL'INNOCENTI, ALESSANDRO;CAPPERUCCI, ANTONELLA;
2005
Abstract
Abstract: Reactions of hexamethyldisilathiane (HMDST) with carbonyl compounds under the catalytic activity of CoCl2.6H2O or trimethylsilyltriflate leads to a simple and general access to thioal-dehydes 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 -silyl substi-tuted 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, thioformylsi-lanes, unsaturated thioacylsilanes and –stannanes can be obtained in good yields. Ethylenic thioacylsilanes showed an interesting behaviour 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 systemsFile | Dimensione | Formato | |
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