Sulfinyl acetate

Enzyme-mediated hydrolysis of some racemic co-arenesulfinylalkanoic methyl esters, ArSO(CH2) COOMe, using Corynebacterium equi has led to a kinetic resolution in which the unreacted sulfinyl esters are enriched in one enantiomer at the sulfoxide center49. The enantiomeric purity of unreacted sulfinyl acetates and propionate ranges from 90 to 97%. 

SoUadid has introduced a-sulfinyl acetates as reagents for asymmetric aldol reactions.Compound (211) is prepared in good optical purity from the menthyl ester of p-tolylsulfinic acid. The magnesium enolate of (211), prepared by reaction of the sulfrnyl ester with r-butylmagnesium bromide, reacts with aldehydes and ketones to give diastereomeric mixtures of a-sulfinyl-3-hydroxy esters (Scheme 13). No... 

The Knoevenagel and Wittig type reactions have been used for the creation of the 6-bond. The condensation of octadecanal with methyl p-(chlorophenyl)sulfinyl acetate in the presence of piperidine afforded the corresponding acetate after acetylation of the hydroxy group which, after subsequent molibdenum-catalyzed elimination, gives the dienic ester as a 4 1 E,E E,Z mixture. After final amidation, the amide trichonine (13) [40] is obtained (Scheme 2). A similar strategy has been used for the synthesis of piperovatine (21) with total E,E-stereoselectivity [41]. 

Fig.l Frequency of detection of herbicides (red bars) and their transformation products (blue bars) in samples collected from 51 US Midwestern streams during late spring runoff (A) and harvest season runoff (B) [34]. ESA - ethane sulfonic acid OXA - oxanilic acid SAA - sulfinyl acetic acid... 

The AA-sulfinyloxazolidinone reagents were found to be useful in the asymmetric synthesis of a-sulfinyl acetate (18), sulfinate esters (19) and sulfinamides (20). 

Chirality need not reside on a sp carbon atom to be recognized by PSL but can be located on a sulfur atom (Scheme 2.64). Thus, optically pure aryl sulfoxides were obtained by lipase-catalyzed resolution of methyl sulfinyl acetates [458] in a biphasic medium containing toluene. The latter compounds are important starting materials for the synthesis of chiral allylic alcohols via the SPAC reaction. 

The Pummerer rearrangement was reported by Rudolf Pummerer in 1909 when he published a paper in Chemische Berichte. Earlier in the same year, Smythe had reported the reaction of dibenzyl sulfoxide 3 with acetic anhydride and hydrochloric acid to give benzaldehyde 4 and thioacetal 5, among other products. Smythe was apparently unable to explain the product distribution, which was then left to Pummerer do so in his much-cited paper later that year. Pummerer published the reaction of sulfinyl acetic acid 6 with hydrochloric acid to give glyoxylic acid 7. The formal oxidation of the... 

---