Base-Mediated Visible-Light-Driven C-H Arylation of Quinoxalin-2(1H)-Ones in Ethanol.

Prior methods for visible-light-driven C-H arylation of quinoxalin-2(1H)-ones relied on external photocatalysts. Herein, we report a photocatalyst-free approach for this arylation. In this approach, ß-dicarbonyl iodonium ylides, combined with t-BuOK in ethanol, act as aryl precursors, forming electron donor-acceptor (EDA) complexes. These complexes enhance light absorption, facilitating efficient single electron transfer and aryl radical formation. Consequently, various quinoxalin-2(1H)-ones undergo precise and efficient arylation without external photocatalysts. This protocol exhibits excellent tolerance toward diverse functional groups, with mild reaction conditions and eco-friendly solvents, revealing a high Ecoscale value.

Visible Light-Driven Flexible Synthesis of α-Alkylated Glycine Derivatives Catalyzed by Reusable Covalent Organic Frameworks.

Herein, we report a heterogeneous visible light-driven preparation of α-alkylated glycine derivatives. This approach employed a ß-ketoenamine-linked covalent organic framework (2D-COF-4) as the heterogeneous photocatalyst and N-hydroxy phthalimide (NHPI) esters as the alkyl radical sources. Numerous glycine derivatives, including dipeptides, were precisely and efficiently alkylated under visible light-driven reaction conditions. Based on the excellent photoactivity and organic reaction compatibility of 2D-COF-4, this alkylation could proceed flexibly in a green solvent (ethanol) without any other additives. The photocatalyst and phthalimide were fruitfully recycled with a simple workup procedure, revealing a high ecoscale value and low environmental factor (E-factor).

Tunable Rh(III)-Catalyzed C(sp2)-H Bond Functionalization of Aryl Imidates with Cyclic 1,3-Diones: Strategic Use of Directing Groups.

A tunable Rh(III)-catalyzed C(sp2)-H bond functionalization of aryl imidates with cyclic 1,3-diones was developed. With suitable and straightforward reaction condition adjustments, the C-H bond functionalization of diverse aryl imidates with cyclic 1,3-diones occurred smoothly and precisely at room temperature. Accompanied by different directing group transformations, a series of corresponding aryl nitriles, hydrophenanthridin-1(2H)-ones, spiro isoindoles, or hydrophenanthridine-1,6(2H,5H)-diones were synthesized in good yields to provide a rational directing group utilization strategy for the Rh(III)-catalyzed C(sp2)-H bond activation. Control experiments and primary mechanistic studies revealed that solvent effects and functional group electronic effects might influence the reaction's selectivity.