2
HighlightsBoth enantiomers of sulforaphane and six homologues were obtained. The ability of the synthesized compounds to activate the Nrf2 is studied The cytotoxic activity of the analogues against cancer and healthy cells is reported.
An improved method for the tert‐butanesulfinylation of diacetone glucose with tert‐butanesulfinyl chloride is reported. The method is based on a beneficial effect of catalytic DMAP, which enhances both the rate of the reaction and the enantioselectivity of the process to give (RS)‐diastereomer 2RS with a 94 % de and in quantitative yield. (RS)‐DAG sulfinate ester 2RS is an excellent intermediate for the synthesis of enantiopure tert‐butyl sulfoxides. Grignard agents and organolithium reagents can displace smoothly the diacetone glucose moiety to give synthetically relevant enantiopure sulfoxides, including highly functionalized derivatives, in high yields and with high enantioselectivities. (RS)‐DAG sulfinate ester 2RS is also an excellent N‐sulfinylating agent; simple addition of LiHMDS (lithium hexamethyldisilazide) in THF gives (SS)‐tert‐butanesulfinamide, and N‐tert‐butanesulfinylimines are then formed in a two‐step one‐pot manner. N‐Alkylated tert‐butanesulfinamides are formed by the condensation of 2RS with lithium amides.
Monosulfinamides and C(2)-symmetric bis-sulfinamides are convenient neutral chiral promoters in the allylation of acyl hydrazones, the nature of the spacer and the substituent at the sulfinyl sulfur are key elements for the enantioselectivity of the process.
A detailed study on the diastereoselective oxidation of 1-thio-β-D-glucopyranosides is reported. It has been shown that the sense and the degree of stereochemical outcome of the oxidation are highly dependent on the substituent of the sulfur and on the protective group of the C2-OH. In the case of thioglycosides with a bulky aglycone, the mesylation of C2-OH has a significant effect on the stereochemical outcome of the oxidation, affording the usually less favoured RS sulfoxide as a single diastereoisomer. The absolute configuration of the final sulfinyl glycosides was ascertained by NMR analysis and corroborated by X-ray crystallography.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.