92316-76-2Relevant articles and documents
Iron corroles and porphyrins as very efficient and highly selective catalysts for the reactions of α-diazo esters with amines
Aviv, Iris,Gross, Zeev
, p. 951 - 953 (2006)
Iron corroles and porphyrins catalyze the reactions of amines with ethyl diazoacetate extremely efficiently, leading to complete and rapid conversion into N-substituted glycine ethyl esters by simultaneous addition of the substrates to the catalysts. The selectivity toward activation of the NH bonds is remarkable and quite different from other catalysts. Georg Thieme Verlag Stuttgart.
Iron(III) corroles and porphyrins as superior catalysts for the reactions of diazoacetates with nitrogen- or sulfur-containing nucleophilic substrates: Synthetic uses and mechanistic insights
Aviv, Iris,Gross, Zeev
scheme or table, p. 3995 - 4005 (2009/05/26)
A thorough mechanistic investigation has been performed on the reactions of primary and secondary amines with diazoacetates, which proceed uniquely quickly and efficiently when catalyzed by iron(III) corroles and porphyrins. Two major differences in relation to other metal-based catalysts are that the iron complexes are not poisoned by excess amine and that metal-carbene intermediates are apparently not involved in the reaction pathway. The results instead point towards nitrogen ylide intermediates formed by nucleophilic attack of the amines on diazoacetate-coordinated iron complexes. Nitrogen ylides are also formed when allyl- and propargylsubstituted tertiary amines react with diazoacetates, a scenario that smoothly leads to 2,3-rearrangement reaction products with catalytic amounts of the iron(III) complexes. Similar findings regarding the superiority of the iron-(III) complexes (in terms of catalyst loading, chemical yields, and reaction conditions) were obtained with thiols (S-H insertion) and sulfides (2,3-rear-rangement reactions), which suggest similar mechanisms operate in these cases.
