Epoxy vinyl sulfoxides

Table 1. Reaction of Cyanocuprate Reagents with Epoxy Vinyl Sulfoxides...

Heterocycle openings. a,p-Epoxy silanes fiimish P-hydroxy silanes due to the attack of cuprate reagents at the a-carbon. The regioselectivity for the reaction of methyl ( J-4,5-epoxypent-2-enoate with arylcopper is dependent on the presence or absence of BF,. The S 2 pathway giving the a-aryl esters becomes significant with the added Lewis acid. The Sf 2 products are observed in the reaction of epoxy vinyl sulfoxides with... 

The synthesis of the preceding vinyl amino sulfone offers a very good example of a stereospecific sulfide-directed epoxidation (Scheme 76).Oxidation of optically active sulfide alcohol (12 readily made from epoxycyclopentadiene and resolved) with MCPBA affords the corresponding sulfoxide, which is in equilibrium with the sulfenate ester. Treatment with pyridine hydrobromide and then phenyl disulfide and bromine gives the bromodiol (13), which is simply cyclized to the epoxide with aqueous sodium hydroxide solution (83% overall yield from the sulfoxide). Treatment of the P-epoxy sulfone with DBU followed by in situ silylation with f-butyldiphenylsilyl chloride affords an 86% yield of vinyl sulfone (14). Mesylation of the alcohol moiety followed by immediate treatment with dimethylamine produces the amino vinyl sulfone via a syn Sn2 substitution. ... 

Solvents used for paint removal are able to dissolve or considerably swell physically drying binders (e.g., vinyl chloride copolymers, cellulose nitrate, polyacrylates) and chemically cross-linked coatings (e.g., oil-based paints, dried alkyd resins, cross-linked polyester-melamine resins, cross-linked epoxy and isocyanate coatings) [14.237]. A combination of dichloromethane with low-boiling ketones or esters is particularly suitable. Small amounts of high-boiling solvents with a low volatility (e.g., tetrahydronaphthalene, solvent naphtha, methyl benzyl alcohol, or benzyl alcohol) are added to these mixtures to retard evaporation and increase the solvency. Modern paint removers do not contain chlorinated hydrocarbons, they are formulated on the basis of high boilers (e.g., dimethylformamide, dimethyl sulfoxide, propylene carbonate, and yV-methylpyrrolidone) in combination with alcohols and aromatics, or consist of aqueous, frequently alkaline or acidic systems. 

The P450s catalyze a variety of reactions, including hydroxylation, epoxidation, peroxidation, sulfoxidation, dealkylation, deamination, etc., depending on the substrate structures. Many substrates, including alkenes, aromatic hydrocarbons, heterocycles, vinyl halides, e yl carbamate, vinyl nitrosamines, and aflatoxin Bl, have been epoxi-dized with good stereoselectivities by the membrane-boimd mammalian P450s [29]. 

---