Triazole-Based Anion-Binding Catalysis for the Enantioselective Dearomatization of N-Heteroarenes with Phosphorus Nucleophiles.

Autor: Fischer T; Institute for Organic Chemistry, University of Regensburg, Universitätsstr. 31, 93053, Regensburg, Germany., Duong QN; Institute for Organic Chemistry, University of Regensburg, Universitätsstr. 31, 93053, Regensburg, Germany., García Mancheño O; Institute for Organic Chemistry, University of Regensburg, Universitätsstr. 31, 93053, Regensburg, Germany.; Straubing Center of Science for Renewable Resources, 94315, Straubing, Germany.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2017 May 02; Vol. 23 (25), pp. 5983-5987. Date of Electronic Publication: 2017 Feb 16.
DOI: 10.1002/chem.201605660
Abstrakt: The first enantioselective synthesis of chiral heterocyclic α-amino phosphonates by nucleophilic dearomatization of quinolines and pyridines using an anion-binding organocatalysis approach is described. Chiral tetrakistriazoles were employed as efficient hydrogen-bond donor catalysts by forming a chiral close ion-pair with the in situ formed N-acyl salts and 2,2,2-trichlorethoxycarbonyl chloride (TrocCl). The ion-pair was subsequently treated with various phosphorus nucleophiles, such as silyl-protected dialkyl- and trialkylphosphites. Thus, the corresponding products were obtained in complete or high regioselectivities and up to 97:3 e.r. for quinolines or up to 89:11 e.r. for the more challenging pyridine substrates. This method allows for rapid access to substituted chiral cyclic α-amino phosphonates, which can be easily transformed into phosphonic acid derivatives.
(© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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