Thiopropenoylstannanes: The First Access to the Class of Thioacylstannanes

Degl’Innocenti, Alessandro; Capperucci, Antonella; Nocentini, Tiziano; Biondi, Simona; Fratini, Valentina; Castagnoli, Giulio; Malesci, Irene

doi:10.1055/s-2004-832806

Cited by 15 publications

(5 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The structure of the so obtained trithiepanes 28 was established by NMR and mass spectra analysis, and by comparison with the literature data described for analogous derivatives. 44g,45a In particular, while 1 H NMR spectra appeared to be second-order spectra, 13 C NMR showed signals in agreement with the proposed symmetric structure, whereas all carbon atoms are differentiated in the unsymmetrical 3,6-disubstituted trithiepane, due to the missing simmetry plane.…”

Section: Functionalization Of Different Electrophiles With Organoselesupporting

confidence: 56%

“…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: 99%

See 1 more Smart Citation

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: Functionalization Of Different Electrophiles With Organoselesupporting

confidence: 56%

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

confidence: 99%

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

“…Thus reaction of trimethylstannyl allene 46 with HMDST in the presence of CoCl 2 ·6H 2 O at -78°C led to isolation of compound 47, generated through the cycloaddition of the a,b-unsaturated thioacylstannane with the in situ formed thioacetaldehyde, 76 as already observed with the analogue thioacylsilanes (Scheme 16). 69…”

Section: Ab-unsaturated Thioacylstannanesmentioning

confidence: 67%

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

“…105 Reaction of stannylated allenes with bis-(trimethylsilyl) sulfide-CoCl 2 Á 6H 2 O afforded the first example of the synthesis Reaction Procedure (Scheme 5.34): In a Schlenk tube equipped with a stirrer bar were placed a,b-unsaturated imine (0.20 mmol), alkyne (0.24 mmol), P(3-ClC 6 H 4 ) 3 (7.3 mg, 0.020 mmol, 10 mol%), CoBr 2 (0.067 M solution in THF, 0.15 mL, 0.010 mmol, 5 mol%) and THF (0.47 mL). To the mixture was added iPrMgBr (0.89 M in THF, 51 mL, 0.045 mmol, 22.5 mol%) at room temperature.…”

Section: Six-membered and Other Heterocyclesmentioning

confidence: 97%

CHAPTER 5. Cobalt-Catalyzed Heterocycle Synthesis

2014

Catalysis Series

View full text Add to dashboard Cite

Cobalt has the chemical configuration [Ar]4s 2 3d 7 and has oxidation states Co(II) and Co(III). Cobalt has many applications in a wide range of areas. In materials, cobalt is primarily used as the metal, for example, in the preparation of magnetic, wear-resistant and high-strength alloys. In biology, cobalt is the active center of coenzymes called cobalamins, the most common example of which is vitamin B 12 . As such, it is an essential trace dietary mineral for all animals. Cobalt in inorganic form is also an active nutrient for bacteria, algae and fungi. In chemistry, various cobalt compounds are used as oxidation catalysts in chemical reactions. Cobalt acetate is used for the conversion of xylene to terephthalic acid, the precursor to the bulk polymer poly(ethylene terephthalate). Typical catalysts are the cobalt carboxylates (known as cobalt soaps). They are also used in paints, varnishes and inks as 'drying agents' through the oxidation of drying oils. The same carboxylates are also used to improve the adhesion of steel to rubber in steel-belted radial tires. Cobalt-based catalysts are also important in reactions involving carbon monoxide. In this chapter, the applications of cobalt catalysts in the synthesis of heterocycles is discussed. Five-Membered HeterocyclesIn 1986, Pattenden and co-workers reported a cobalt-promoted oxidative freeradical cyclization of alkyl bromides, 1 by which functionalized butyrolactones were selectively formed in good yields. In 1990, a convenient method for the stereoselective preparation of trans-2-hydroxymethyltetrahydrofurans by the oxidative cyclization of 5-hydroxy-1-alkenes was developed by Inoki and Mukaiyama. 2 They used bis(1-morpholinocarbamoyl-4,4-dimethyl-1,3-pentanedionato)cobalt(II) [Co(modp) 2 ] as the catalyst with molecular oxygen as the RSC Catalysis Series No.

show abstract

Thiopropenoylstannanes: The First Access to the Class of Thioacylstannanes

Cited by 15 publications

References 8 publications

Silicon-Assisted Synthesis and Functionalization of Sulfurated and Selenated Compounds

Silicon-Assisted Synthesis and Functionalization of Sulfurated and Selenated Compounds

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

CHAPTER 5. Cobalt-Catalyzed Heterocycle Synthesis

Contact Info

Product

Resources

About