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The Disappearing Director: The Case of Directed N ‐Arylation via a Removable Hydroxyl Group
Author(s) -
Andrzejewska Magdalena R.,
Vuram Prasanna K.,
Pottabathini Narender,
Gurram Venkateshwarlu,
Relangi Siva Subrahmanyam,
Korvinson Kirill A.,
Doddipalla Raju,
Stahl Lothar,
Neary Michelle C.,
Pradhan Padmanava,
Sharma Somesh,
Lakshman Mahesh K.
Publication year - 2018
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.201701611
Subject(s) - chemistry , benzotriazole , aryl , reagent , medicinal chemistry , amine gas treating , group (periodic table) , tautomer , stereochemistry , organic chemistry , alkyl
A facile and broadly applicable method for the regiospecific N ‐arylation of benzotriazoles is reported. Copper‐mediated reactions of diverse 1‐hydroxy‐1 H ‐benzotriazoles with aryl boronic acids lead to 1‐aryl‐1 H ‐benzotriazole 3‐oxides. A N 1‐OH→ N 3 prototropy in the 1‐hydroxy‐1 H ‐benzotriazoles is plausibly the underlying basis, where the tautomer is captured by the boronic acid, leading to C−N (not C−O) bond formation. Because the N−O bond in amine N ‐oxides and 1‐hydroxy‐1 H ‐benzotriazoles can be easily reduced by diboron reagents such as (pinB) 2 and B 2 (OH) 4 , exposure of the 1‐aryl‐1 H ‐benzotriazole 3‐oxides to B 2 (OH) 4 then leads to facile reduction of the N−O bond resulting in diverse, regiospecifically‐arylated benzotriazoles. Thus, the N ‐hydroxyl group in 1‐hydroxy‐1 H ‐benzotriazoles acts as a disposable arylation director.