Synthesis of naturally occurring (2S,3S)-(+)-aziridine-2,3-dicarboxylic acid.

An improved synthesis of aziridine-2,3-dicarboxylates via azido alcohols—epimerization studies

“…With NaN 3 , the diastereomers of these azido alcohols, the (2R,3R)-synand (2S,3S)-syn-3-azido-2-hydroxysuccinates 6b are formed as by-products which have to be separated by column chromatography, otherwise, the following ring closure to trans-(2S,3S)-and trans-(2R,3R)-aziridine-2,3-dicarboxylate 7b, respectively, with triphenylphosphine would be accompanied by formation of the cis-(2S,3R)-aziridine. 14,29,30 The maximum overall yield of this five step aziridine synthesis is about 30%. The reasons for complete epimerization using NaN 3 as azide donor and an appropriate alcohol as solvent 14,29 during the ring opening of the epoxide, however, remained unclear.…”

Catalytic Asymmetric Aziridination of α,β‐Unsaturated Aldehydes

“…(7)]. [41] It was successfully executed by oxidation and in situ esterification of the b-formyl azirdine product, which had been generated by the chiral amine 10-catalyzed aziridination of (E)-ethyl 4-oxobut-2-enoate 1 j in methanol. In fact, this protocol gave the protected natural product (2S,3S)-(+)-aziridine-2,3-dicarboxylic acid derivative 18 k in 33 % yield (two steps) with > 19:1 d.r.…”

Inhibition of cysteine proteases by peptides containing aziridine-2,3-dicarboxylic acid building blocks

“…This synthetic pathway leads to (R,R) and (S,S) diethyl oxirane-2,3-dicarboxylate, respectively, as intermediates. 16 Nucleophilic ring opening with NaN 3 /NH 4 Cl and subsequent ring closure under Mitsunobu conditions with Ph 3 P according to the method described by Legters et al 17 gave the reverse configured aziridines together with a small amount of (R,S) product resulting from epimerization during syntheses of azido alcohols caused by nucleophilic azide exchange. 17 Racemic (S,SϩR,R) benzyl ethyl aziridine-2,3-dicarboxylate (4a؉b) was prepared by Michael-type addition of diphenyl sulfimide 18 to benzyl ethyl fumarate (Scheme 2).…”