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Expanding the Versatile Reactivity of Diazido Malonic Acid Esters and Amides: Decarboxylation and Imine Formation
Author(s) -
Borghi Federica,
Çelik Ibrahim E.,
Biallas Phillip,
Mittendorf Fabia,
Kirsch Stefan F.
Publication year - 2020
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202000641
Subject(s) - chemistry , malonic acid , diethyl malonate , decarboxylation , malonate , imine , reactivity (psychology) , sodium azide , azide , organic chemistry , combinatorial chemistry , catalysis , medicine , alternative medicine , pathology
Herein, we advance our understanding on the divergent reaction pathways that are possible, starting from diazido diethyl malonate (easily generated through the oxidative diazidation of diethyl malonate with iodine and sodium azide in DMSO at room temperature): when treated with amines, diazidated malonamides are rapidly formed, many of which then undergo a formal substitution reaction with alkylamines leading to imino malonamides under basic conditions. Using the established conditions of CuAAC click reactions with terminal alkynes, the diazidated malonamides are alternatively transformed into their corresponding bistriazole derivatives, a reaction that is also achievable with diazido diethyl malonate. We now demonstrate that the malonic diester bistriazoles undergo a smooth decarboxylation in the presence of amines, creating novel bistriazole variants derived from acetamides. All protocols presented herein are experimentally simple and enhance the variety of products obtainable from malonic acid derivatives.