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Triazole‐Based Anion‐Binding Catalysis for the Enantioselective Dearomatization of N ‐Heteroarenes with Phosphorus Nucleophiles
Author(s) -
Fischer Theresa,
Duong QuiNhi,
García Mancheño Olga
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201605660
Subject(s) - enantioselective synthesis , nucleophile , chemistry , pyridine , catalysis , organocatalysis , hydrogen bond , combinatorial chemistry , silylation , phosphorus , medicinal chemistry , organic chemistry , molecule
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.