Highly Enantioselective Nucleophilic Dearomatization of Pyridines by Anion-Binding Catalysis

Angewandte Chemie - International Edition

Volumn 54, Issue 30, 2015, Pages 8823-8827

  García Mancheño, Olga ^a,b   Asmus, Sören ^a   Zurro, Mercedes ^a   Fischer, Theresa ^a  

^a UNIVERSITY OF REGENSBURG   (Germany)

^b TECHNICAL UNIVERSITY OF MUNICH   (Germany)

Author keywords

anion binding catalysis; dearomatization; enantioselectivity; pyridine; triazoles

Indexed keywords

AROMATIZATION; BINS; CATALYSIS; CATALYSTS; ENANTIOSELECTIVITY; IONS; REGIOSELECTIVITY;

ANION BINDING; CHIRAL HETEROCYCLES; DEAROMATIZATION; IONIC INTERMEDIATES; SIX-MEMBERED RINGS; SYNTHETIC APPROACH; SYNTHETIC METHODS; TRIAZOLES;

PYRIDINE;

ANION; PYRIDINE DERIVATIVE; TRIAZOLE DERIVATIVE;

CATALYSIS; CHEMISTRY; STEREOISOMERISM;

ANIONS; CATALYSIS; PYRIDINES; STEREOISOMERISM; TRIAZOLES;

EID: 84941000723     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201502708     Document Type: Article

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59. A 2 mmol reaction with the recycled catalyst 1 a led to 5 a in similar good results: 84 % yield and 98:2 e.r.
60. Only traces of 1,2-dihydropyridines 5 i-k, which also present the typically high 91:9-94:6 e.r., could be detected by HPLC. This substrate-dependent change on the regioselectivity is still not well understood. The catalyst provided relatively high stereocontrol in 6 i-k compared to 6 a (54:46 e.r.), which might be attributed to a less efficient but still active action of the catalysts with 3 i-k vs. the mainly competitive achiral background reaction with 3 a towards the C4 addition.
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62. 1H NMR characteristic signal of the H at the new stereocenter at 3.2-3.6 ppm (vs. aprox. 5.0 ppm in 5 (H in α-position to the N-atom)); 2) 2D-NMR and NOESY experiments on 11 also confirmed this regioisomeric structure.
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64. D value of a known compound (see the Supporting Information).