Dithioketalization

Me2CH(CH2)20NO, CH2CI2, 25°, 15 min H2O, 63-93% yield." Isoamyl nitrite cleaves aromatic dithioacetals in preference to aliphatic dithioace-tals, and dithioacetals in preference to dithioketals. It also cleaves 1,3-oxathiolanes (1 h, 65-90% yield). 

Methyliodobenzene difluoride cleaves aryl dithioketals. The reactions are conducted in dichloromethane solutions at 0 °C to give gem-difluoro compounds in 65-90% yields [4 (equation 6)... 

Scheme 3. Construction of didehydrooxocane systems by the hydroxy dithioketal cyclization.

It is important to emphasize that the hydroxy dithioketal cyclization can be conducted under mild reaction conditions and can be successfully applied to a variety of substrates.15 However, the utility of this method for the synthesis of didehydrooxocane-contain-ing natural products requires the diastereoselective, reductive removal of the ethylthio group. Gratifyingly, treatment of 13 with triphenyltin hydride and a catalytic amount of the radical initiator, azobisisobutyronitrile (AIBN), accomplishes a homolytic cleavage of the C-S bond and furnishes didehydrooxocane 14 in diastereo-merically pure form (95 % yield), after hydrogen atom transfer. 

Cyclic dithioketals and acetals represent another important class of sulfur containing chiral auxiliaries, which are available in chiral form by biooxidation. Biotransformations were performed on a preparative scale using whole-cells (wild type and recombinant) and isolated enzyme. Again, enantiocomplementary oxidation of unsubstituted dithianes (linear and cyclic, R = H) was observed when using and CPMOcomo (Scheme 9.28) [211,212]. Oxygenation of functionalized substrates (R = substituted alkyl) with gave preferably trans... 

The thiophosphate phorate is degraded in aqueous solutions at pH 8.5 to yield diethyl sulfide and formaldehyde, which are formed by nucleophilic attack either at the P = S atom or the methylene dithioketal carbon atom (Hong and Pehkonen 1998). 

Liu (12) had reported that III could be conveniently separated from IV by selective thioketalization to V followed by purification by column chromatography. Accordingly, a mixture of approximately 70% III and 30% IV (60.9 g) was treated with 1,2-ethanedithlol (50 ml) and boron trifluoride etherate (6 ml). The crude product was distilled under reduced pressure to yield 45.1 g (54.4%, 77.6% based upon III as starting material) of crude V, sufficiently pure for the next step. Column chromatography of lower boiling impure fractions furnished the dithioketal VI (10% yield), unreacted IV, and additional V. ... 

It has been found that dithioketals when refluxed with moderately active Ra-Ni in ketone solvents yield olefins as the main products.416 Ethylene dithio-acetal was refluxed in benzene-containing ethanol with Ra-Ni for 20 hours and was converted to olefin (Scheme 4.119).417... 

Allyl Halides, Sulfides, Amines, Acetals and Dithioketals. 132... 

Interaction of an electrophilic carbene or carbenoid with R—S—R compounds often results in the formation of sulfonium ylides. If the carbene substituents are suited to effectively stabilize a negative charge, these ylides are likely to be isolable otherwiese, their intermediary occurence may become evident from products of further transformation. Ando 152 b) has given an informative review on sulfonium ylide chemistry, including their formation by photochemical or copper-catalyzed decomposition of diazocarbonyl compounds. More recent examples, including the generation and reactions of ylides obtained by metal-catalyzed decomposition of diazo compounds in the presence of thiophenes (Sect. 4.2), allyl sulfides and allyl dithioketals (Sect. 2.3.4) have already been presented. 

Desulfuration.1 This complex as such or in combination with 2,2 -bipyridyl (bpy) or triphenylphosphine (a NiCRAL) can effect desulfuration of heteroarenes. aryl thioethers, dithioketals, sulfoxides, or sulfones in DME or THF at 63° in 1.5-30 hours. NiCRA is sufficient for aryl thioethers, dithioketals, but NiCRALs are more efficient for desulfuration of heteroarenes. Yields can be comparable with those obtained with Raney nickel. 

Desulfuration-dimerization of dithioketals.1 Dithioketals when refluxed with W(CO)6 in chlorobenzene are converted into the corresponding dimeric alkenes. 

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