An easy access to α,β-unsaturated thioacylsilanes: a useful route to silylated 1,2-dithiins

Capperucci, Antonella; Degl’Innocenti, Alessandro; Biondi, Simona; Nocentini, Tiziano; Rinaudo, Giuseppe

doi:10.1016/s0040-4039(03)00445-3

Cited by 27 publications

(5 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…9 Of particular interest was the synthesis of a,b-ethylenic thioacylsilanes from the corresponding silylated allenes, which led to the formation of polyfunctionalized 1,2-dithiins 1, arising from a head-to-head self-dimerization reaction (Scheme 2). 12 In a similar way, the procedure was efficient also for the synthesis of unsaturated thioacylstannanes, through the reaction of stannyl allenes with HMDST (Scheme 2). 13 Propenoylstannanes showed a peculiar behaviour, being able to react as thiabutadienes towards in situ generated thioaldehydes.…”

Section: Bis(silyl)sulfide In the Synthesis Of Thiocarbonyl Compoundsmentioning

confidence: 94%

Silicon-Assisted Synthesis and Functionalization of Sulfurated and Selenated Compounds

Capperucci

Tanini

2015

Phosphorus, Sulfur, and Silicon and the Related Elements

Self Cite

View full text Add to dashboard Cite

The synthetic potential of thiosilanes and selenosilanes toward various electrophiles is described, focusing on the synthesis of a representative range of thiocarbonyl, selenocarbonyl, b-functionalized compounds and acyl-seleno derivatives. Reactions of silyl chalcogenides with epoxides, episulfides and aziridines allowed the synthesis of b-hydroxy, b-mercapto and b-amino thiols, as well as of b-substituted selenides and diselenides. A peculiar behaviour was observed in the reaction with episulfides, leading to 7-membered trithia-and dithiaseleno-heterocycles. Furthermore, carbodesilylation of a-heterosubstituted organosilanes provided a smooth access to benzothiophene and benzofuran-derivatives. Downloaded by [University of Montana] at 16:41

show abstract

Section: Bis(silyl)sulfide In the Synthesis Of Thiocarbonyl Compoundsmentioning

confidence: 94%

Silicon-Assisted Synthesis and Functionalization of Sulfurated and Selenated Compounds

Capperucci

Tanini

2015

Phosphorus, Sulfur, and Silicon and the Related Elements

Self Cite

View full text Add to dashboard Cite

show abstract

“…In addition, disilathianes also play a significant role in the construction of sulfur-containing heterocyclic molecules via C–S bond formations to incorporate a sulfur atom into the ring structure. 2a d g h 6a e 9 Among S -heterocycles, isothiochromenes and their derivatives have gained considerable interest due to their attractive biological activity. 10 For the synthesis of isothiochromenes, the early study by Pfeffer et al described a palladium-mediated multi-step sequence from iodobenzyl methyl sulfides with internal alkynes involving an alkyne insertion to a cyclopalladated complex.…”

Section: Table 1 Optimization Of Reaction Conditions ...mentioning

confidence: 99%

Disilathiane as a Sulfur Source for the Construction of Isothiochromenes and Benzo[b]thiophenes by Copper-Catalyzed endo-Selective Hydrothiolation

Nakajima¹,

Takeuchi²,

Oomori³

et al. 2022

Synthesis

View full text Add to dashboard Cite

A copper-catalyzed construction of isothiochromenes and benzo[b]thiophenes via annulation with 1,1,1,3,3,3-hexamethyldisilathiane as a sulfur source is described. In the isothiochromene synthesis, the use of the disilathiane as a sulfur source successfully controls the regioselectivity of cyclization to afford the isothiochromene as a sole product. The present strategy can be applied to synthesis of 2-aryl/2-alkylbenzo[b]thiophenes.

show abstract

“…Being unsat-urated acylsilanes obtainable through the hydrolysis of the corresponding silylated allenes, the same reaction could have hold in the presence of HMDST to afford the wanted a,b-ethylenic silyl thioketones. So, silylated allenes were reacted with HMDST and 2,3dimethylbutadiene, in the presence of CoCl 2 •6H 2 O, and in these conditions the reaction afforded 1,2-dithiins as main products, together with minor amounts of isomeric 1,3dithiins (Table 13), 69 thus evidencing the formation of the transient thiopropenoylsilane, which undergoes preferably self-dimerization reaction, thus confirming the tendency of such molecules to behave as thiabutadienes with reactive dienophiles in hetero Diels-Alder reactions. 70 It is interesting to note that, differently from what observed in the case of a,b-unsaturated thioaldehydes, the presence of the silyl group led to the formation of the adduct with the diene only in trace amounts (Table 13, entry 1).…”

Section: Scheme 11 Synthesis Of B-trimethylsilyl-thiopropinoylsilanementioning

confidence: 99%

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

Degl’Innocenti¹,

Capperucci²,

Castagnoli³

et al. 2005

Synlett

Self Cite

View full text Add to dashboard Cite

Reactions of hexamethyldisilathiane (HMDST) with carbonyl compounds under the catalytic activity of CoCl 2 ·6H 2 O 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 CF 3 SO 3 SiMe 3 in reactions with cyclohexadiene allows a stereopredetermined access to either the endo-or the exo-isomer. Furthermore, on using b-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.

show abstract

An easy access to α,β-unsaturated thioacylsilanes: a useful route to silylated 1,2-dithiins

Cited by 27 publications

References 49 publications

Silicon-Assisted Synthesis and Functionalization of Sulfurated and Selenated Compounds

Silicon-Assisted Synthesis and Functionalization of Sulfurated and Selenated Compounds

Disilathiane as a Sulfur Source for the Construction of Isothiochromenes and Benzo[b]thiophenes by Copper-Catalyzed endo-Selective Hydrothiolation

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

Contact Info

Product

Resources

About