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Nitrone/Imine Selectivity Switch in Base‐Catalysed Reaction of Aryl Acetic Acid Esters with Nitrosoarenes: Joint Experimental and Computational Study
Author(s) -
Volpe Chiara,
Meninno Sara,
Roselli Angelo,
Mancinelli Michele,
Mazzanti Andrea,
Lattanzi Alessandra
Publication year - 2020
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.202000855
Subject(s) - chemistry , moiety , aryl , imine , nitroso compounds , catalysis , acetic acid , nitrone , aldol reaction , methylene , nitroso , selectivity , combinatorial chemistry , photochemistry , organic chemistry , cycloaddition , alkyl
Herein we report a mild and diastereoselective access to ketonitrones by reacting easily available aryl acetic acid esters and other active methylene compounds, with nitrosoarenes under catalytic loading of 2‐ tert ‐butylimino‐2‐diethylamino‐1,3‐dimethylperhydro‐1,3,2‐diazaphosphorine (BEMP) at room temperature. Depending on the substitution pattern and nature of the aryl moiety, a switch toward the formation of imines can be observed. The mechanistic framework is put to scrutiny by experimental and theoretical studies, pointing to the formation of a nitroso aldol intermediate, whose fate toward one of the competing pathways, namely hydride transfer or elimination, would depend upon the NOH/CH α relative acidities.