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.

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).