Visible‐Light‐Mediated Decarboxylation/Oxidative Amidation of α‐Keto Acids with Amines under Mild Reaction Conditions Using O₂

Abstract

Photochemistry has ushered in a new era in the development of chemistry, and photoredox catalysis has become a hot topic, especially over the last five years, with the combination of visible-light photoredox catalysis and radical reactions. A novel, simple, and efficient radical oxidative decarboxylative coupling with the assistant of the photocatalyst [Ru(phen)3 ]Cl2 is described. Various functional groups are well-tolerated in this reaction and thus provides a new approach to developing advanced methods for aerobic oxidative decarboxylation. The preliminary mechanistic studies revealed that: 1) an SET process between [Ru(phen)3 ](2+) * and aniline play an important role; 2) O2 activation might be the rate-determining step; and 3) the decarboxylation step is an irreversible and fast process.

Stabilization of Two Radicals with One Metal: A Stepwise Coupling Model for Copper-Catalyzed Radical–Radical Cross-Coupling

“…Here, we describe our theoretical understanding of transition metal-catalyzed radical–radical cross-coupling reactions434445. As shown in Fig.…”

Catalyst-free direct decarboxylative coupling of α-keto acids with thiols: a facile access to thioesters

“…20 Therefore, this simple and catalyst-free synthesis protocol could be expected as a practical and efficient method to access various thioesters. As shown in Scheme 4, the present reaction could afford 1.03 g of 3a in 96 % yield under the standard conditions, without any significant loss of its efficiency.…”

“…(Scheme 1, a). 20 Very recently, we developed silver-mediated and catalyzed 5 radical pathways for the synthesis of coumarins and chalcones using α-keto acids as coupling partners. 20 Very recently, we developed silver-mediated and catalyzed 5 radical pathways for the synthesis of coumarins and chalcones using α-keto acids as coupling partners.…”

Durch sichtbares Licht induzierte decarboxylierende Funktionalisierung von Carbonsäuren und ihren Derivaten

“…[9] Gegen Ende des Jahres 2013 gelang Lei et al mit der lichtinduzierten decarboxylierenden Amidierung von a-Ketosäuren ein ermutigender Durchbruch, durch den ein neuartiger und effizienter Zugang zu einer Vielzahl an Amiden mit guten Ausbeuten geschaffen wurde (Schema 1). [10] (Schema 5). [13] Das Verfahren bietet eine optimale Plattform zur Neubildung von C-C-Bindungen und Bei einer anderen beeindruckenden decarboxylierenden Vinylierung von a-Aminosäuren, die die Arbeitsgruppe um MacMillan entwickelt hat, spielt eine radikalische konjugierte Addition eine Schlüsselrolle (Schema 6).…”