60178-20-3Relevant academic research and scientific papers
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.
Tin-free reductive photochemical carboxymethylation of olefins with α- alkylthioacetates
Deng, Lisa X.,Kutateladze, Andrei G.
, p. 7829 - 7832 (2007/10/03)
An efficient tin-free reductive photochemical carboxymethylation of olefins with α-alkylthioacetates is developed, which (a) is an experimentally simple technique furnishing substituted derivatives of fatty acids in moderate to good yields, (b) is compatible with polar/protic functional groups and solvents, (c) does not require a special reducing reagent, (d) is fairly insensitive to the presence of dissolved oxygen and, generally, does not require degassing prior to irradiation. The critical feature of the mechanism is the 'reluctance' of short-lived MeS' to group- transfer, resulting in hydrogen abstraction from the media.
Insertion of ethyl diazoacetate into N-H and S-H bonds catalyzed by ruthenium porphyrin complexes
Galardon, Erwan,Le Maux, Paul,Simonneaux, Gerard
, p. 2455 - 2456 (2007/10/03)
Ruthenium porphyrin complexes catalyze insertion of ethyl diazoacetate into sulfur-hydrogen and nitrogen-hydrogen bonds under mild conditions and with reasonable to very good yields.
DECOMPOSITION OF S-ALKYLISOTHIOURONIUM SALTS UNDER ANHYDROUS CONDITIONS - APPLICATION TO A FACILE PREPARATION OF NONSYMMETRICAL DIALKYL SULFIDES
Luzzio, Frederick A.,Little, Arthur D.
, p. 209 - 214 (2007/10/02)
5-Alkylisothiouronium salts are decomposed with sodium ethoxide/ethanol or sodium hydride/tetrahydrofuran to the salt of the corresponding thiols which are trapped by various electrophiles to yield nonsymmetrical dialkyl sulfides.
