Photoredox-Catalyzed Cascade of o-Hydroxyarylenaminones to Access 3-Aminated Chromones.

Reported herein is a photoredox-catalyzed amination of o-hydroxyarylenaminones with tert-butyl ((perfluoropyridin-4-yl)oxy)carbamate, a versatile amidyl-radical precursor developed in our laboratory. This work establishes a new cascade pathway for the assembly of a range of 3-aminochromones under mild conditions. Downstream transformations of the obtained 3-aminochromones to construct diverse amino pyrimidines greatly broaden the applications of this photocatalyzed protocol.

TBN-triggered, manipulable annulations of o-hydroxyarylenaminones for divergent syntheses of oximinochromanones and oximinocoumaranones.

Divergent synthesis provides an indispensable route to rapid acquisition of structurally diverse chemical scaffolds from identical starting materials. Herein, we describe unprecedented divergent annulations of o-hydroxyarylenaminones promoted by tert-butyl nitrite (TBN) under mild conditions. Two different types of benzo-oxa-heterocycle, including oximinochromanones and oximinocoumaranones, were smoothly assembled with a broad substrate scope and good functional group compatibility.

Recent progress in the nitration of arenes and alkenes.

Nitro compounds are a predominant class of synthetic intermediates and building blocks for the preparation of a wide range of nitrogen-containing compounds in the chemical industry. As such, impressive progress has been currently made in the nitration of aromatics and olefins with excellent functional group tolerance and site-selectivity. In this mini review, we intend to highlight the regiospecific nitration of arenes and alkenes in various reaction systems. The involved mechanisms are discussed as well.

O-Perhalopyridin-4-yl Hydroxylamines: Amidyl-Radical Generation Scaffolds in Photoinduced Direct Amination of Heterocycles.

Reported herein is the design and synthesis of new O-perhalopyridin-4-yl hydroxylamines as shelf-stable and versatile amidyl-radical precursors. The novel amination reagents can be easily prepared via a single synthetic step from inexpensive commercially available starting materials using monoprotected HONH2 as amino source. The synthetic potency of the developed reagents was well demonstrated by direct amination of a series of quinoxalin-2(1H)-ones and their analogues under photocatalytic conditions, even without any additive and photocatalysts.

Photocatalytic Hydroacylation of Alkenes by Directly Using Acyl Oximes.

Acyl oximes are directly used as the acyl radical precursors in the hydroacylation reactions for the first time. In this work, acyl radicals can be effectively generated via ß-scission of a phosphoranyl radical under photocatalytic conditions. As a result, the hydroacylation of alkenes triggered by the resulting acyl radicals leads to facile syntheses of a range of valuable ketones.