2311-21-9Relevant articles and documents
A simple and convenient synthesis of N-formyl amino acid esters under mild conditions
Duczek,Deutsch,Vieth,Niclas
, p. 37 - 38 (1996)
A variety of amino acid ester hydrochlorides react with cyanomethyl formate at room temperature to give the N-formyl amino acid esters in good yields and without racemization.
Elucidating the Reaction Pathway of Decarboxylation-Assisted Olefination Catalyzed by a Mononuclear Non-Heme Iron Enzyme
Yu, Cheng-Ping,Tang, Yijie,Cha, Lide,Milikisiyants, Sergey,Smirnova, Tatyana I.,Smirnov, Alex I.,Guo, Yisong,Chang, Wei-Chen
supporting information, p. 15190 - 15193 (2018/11/23)
Installation of olefins into molecules is a key transformation in organic synthesis. The recently discovered decarboxylation-assisted olefination in the biosynthesis of rhabduscin by a mononuclear non-heme iron enzyme (P.IsnB) represents a novel approach in olefin construction. This method is commonly employed in natural product biosynthesis. Herein, we demonstrate that a ferryl intermediate is used for C-H activation at the benzylic position of the substrate. We further establish that P.IsnB reactivity can be switched from olefination to hydroxylation using electron-withdrawing groups appended on the phenyl moiety of the analogues. These experimental observations imply that a pathway involving an initial C-H activation followed by a benzylic carbocation species or by electron transfer coupled β-scission is likely utilized to complete C=C bond formation.
Formamide Synthesis through Borinic Acid Catalysed Transamidation under Mild Conditions
Mohy El Dine, Tharwat,Evans, David,Rouden, Jacques,Blanchet, Jér?me
supporting information, p. 5894 - 5898 (2016/04/26)
A highly efficient and mild transamidation of amides with amines co-catalysed by borinic acid and acetic acid has been reported. A wide range of functionalised formamides was synthesized in excellent yields, including important chiral α-amino acid derivatives, with minor racemisation being observed. Experiments suggested that the reaction rely on a cooperative catalysis involving an enhanced boron-derived Lewis acidity rather than an improved Br?nsted acidity of acetic acid. Amide bonds are reputedly difficult to activate due to their high resonance stabilization. An unusual mild activation of dimethylformamide and formamide by borinic acid 1 (see scheme), illustrated by a general formylation of a wide range of amines, including chiral α-amino esters, has been reported.
Transamidation of carboxamides catalyzed by Fe(III) and water
Becerra-Figueroa, Liliana,Ojeda-Porras, Andrea,Gamba-Sánchez, Diego
, p. 4544 - 4552 (2014/06/09)
The highly efficient transamidation of several primary, secondary, and tertiary amides with aliphatic and aromatic amines (primary and secondary) is described. The reaction is performed in the presence of a 5 mol % concentration of different hydrated salts of Fe(III), and the results show that the presence of water is crucial. The methodology was also applied to urea and phthalimide to demonstrate its versatility and wide substrate scope. An example of its use is an intramolecular application in the synthesis of 2,3-dihydro-5H-benzo[b]-1,4- thiazepin-4-one, which is the bicyclic core of diltiazem and structurally related drugs (Budriesi, R.; Cosimelli, B.; Ioan, P.; Carosati, E.; Ugenti, M. P.; Spisani, R. Curr. Med. Chem. 2007, 14, 279-287). A plausible mechanism that explains the role of water is proposed on the basis of experimental observations and previous mechanistic suggestions for transamidation reactions catalyzed by transition metals such as copper and aluminum. This methodology represents a significant improvement over other existing methods; it can be performed in air and with wet or technical grade solvents.