Acceptorless cross-dehydrogenative coupling for C(sp3)-H heteroarylation mediated by a heterogeneous GaN/ketone photocatalyst/photosensitizer system.

Alkanes are naturally abundant chemical building blocks that contain plentiful C(sp3)-H bonds. While inert, the activation of C(sp3)-H via hydrogen atom abstraction (HAT) stages an appealing approach to generate alkyl radicals. However, prevailing shortcomings include the excessive use of oxidants and alkanes that impede scope. We herein show the use of gallium nitride (GaN) as a non-toxic, recyclable, heterogeneous photocatalyst to enable alkyl C(sp3)-H in conjunction with the catalytic use of simple photosensitizer, benzophenone, to promote the desired alkyl radical generation. The dual photocatalytic cycle enables cross-dehydrogenative Minisci alkylation under mild and chemical oxidant-free conditions.

A One-Pot Approach for Bio-Based Arylamines via a Combined Photooxidative Dearomatization-Rearomatization Strategy.

The synthesis of arylamines from renewable resources under mild reaction conditions is highly desired for the sustainability of the chemical industry, where the production of hazardous waste is a prime concern. However, to date, there are very few tools in chemists' toolboxes that are able to produce arylamines in a sustainable manner. Herein, a robust one-pot approach for constructing bio-based arylamines via a combined photooxidative dearomatization-rearomatization strategy is presented. The developed methodology enables the synthesis of structurally complex amines in moderate-to-good isolated yields using biomass-derived phenols, natural α-amino acids, and naphthols under remarkably mild reaction conditions. For the photooxygenation of phenols, a novel chrysazine-based catalyst system was introduced, demonstrating its efficiency for the synthesis of natural products - hallerone, rengyolone, and the pharmaceutically relevant prodrug DHED.

Transition-Metal- and Light-Free Directed Amination of Remote Unactivated C(sp3)-H Bonds of Alcohols.

Due to the great value of amino alcohols, new methods for their synthesis are in high demand. Abundant aliphatic alcohols represent the ideal feedstock for the method development toward this important motif. To date, transition-metal-catalyzed approaches for the directed remote amination of alcohols have been well established. Yet, they have certain disadvantages such as the use of expensive catalysts and limited scope. Very recently, transition-metal-free visible-light-induced radical approaches have emerged as new powerful tools for directed remote amination of alcohols. Relying on 1,5-HAT reactivity, these methods are limited to ß - or δ-amination only. Herein, we report a novel transition-metal- and visible-light-free room-temperature radical approach for remote ß -, γ-, and δ-C(sp3)-N bond formation in aliphatic alcohols using mild basic conditions and readily available diazonium salt reagents.