Understanding and Exploitation of Neighboring Heteroatom Effect for the Mild N-Arylation of Heterocycles with Diaryliodonium Salts under Aqueous Conditions: A Theoretical and Experimental Mechanistic Study.
The mechanism of arylation of N-heterocycles with unsymmetric diaryliodonium salts is elucidated. The fast and efficient N-arylation reaction is interpreted in terms of the bifunctionality of the substrate: The consecutive actions of properly oriented Lewis base and Brønsted acid centers in sufficient proximity result in the fast and efficient N-arylation. The mechanistic picture points to a promising synthetic strategy where suitably positioned nucleophilic and acidic centers enable functionalization, and it is tested experimentally.
Institute of Organic Chemistry, Research Centre for Natural Sciences of the Hungarian Academy of Sciences , Magyar Tudósok Körútja 2, H-1117 Budapest, Hungary.
Tamás
T
Bihari
Institute of Organic Chemistry, Research Centre for Natural Sciences of the Hungarian Academy of Sciences , Magyar Tudósok Körútja 2, H-1117 Budapest, Hungary.
Bence
B
Babinszki
MTA-ELTE "Lendület" Catalysis and Organic Synthesis Research Group, Institute of Chemistry, Eötvös Loránd University , Pázmány Péter sétány 1/a H-1117 Budapest, Hungary.
Zsombor
Z
Gonda
MTA-ELTE "Lendület" Catalysis and Organic Synthesis Research Group, Institute of Chemistry, Eötvös Loránd University , Pázmány Péter sétány 1/a H-1117 Budapest, Hungary.
Szabolcs
S
Kovács
MTA-ELTE "Lendület" Catalysis and Organic Synthesis Research Group, Institute of Chemistry, Eötvös Loránd University , Pázmány Péter sétány 1/a H-1117 Budapest, Hungary.
Zoltán
Z
Novák
Institute of Organic Chemistry, Research Centre for Natural Sciences of the Hungarian Academy of Sciences , Magyar Tudósok Körútja 2, H-1117 Budapest, Hungary.
András
A
Stirling