Abstract
Sterically congested α-tertiary primary amines are ubiquitous substructures in pharmaceutical and agrochemical agents yet are challenging to access. Herein, a straightforward photoredox-catalyzed access to structurally diverse α,α,α-trisubstituted primary amines from denitrogenative alkylarylation or dialkylation of vinyl azides with NHPI esters and cyanoarenes or aryl aldehydes has been developed. The use of vinyl azide as a precursor to a primary amine was enabled by the dual role of Hantzsch ester to form an electron donoracceptor (EDA) complex and serve as a sacrificial reductant. This strategy provides a modular synthesis of α-tertiary primary amines, including unprotected 1,2-amino alcohols, from simple materials with excellent functional group tolerance. The synthetic applicability of this method was demonstrated by streamlined access to 2,2-disubstituted tetrahydroquinolines. Preliminary investigations support two parallel reductive photocatalytic cycles allowing for the denitrogenative alkylarylation or dialkylation of vinyl azides via decarboxylative radical addition followed by hetero-radical cross-coupling between α-amino radicals and aryl anion radicals or ketyl anion radicals.
Original language | English |
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Journal | CCS Chemistry |
Early online date | 25 Jul 2023 |
DOIs | |
Publication status | E-pub ahead of print - 25 Jul 2023 |
Keywords
- photocatalysis
- α-tertiary primary amines
- 1,2-amino alcohols
- vinyl azide
- EDA complex