Ambient Temperature Dehydrogenative C(Ar)–H Carbonylative Lactamization of 2-Arylanilines Using DMF as C1-Source

Abstract

The direct dehydrogenative C−H cleaving carbonylative lactamization of 2-arylanilines promoted by visible light and potassium bases is reported. Solvent DMF acts as the sole carbonyl source in the absence of an oxidant. The irreversible release of hydrogen gas drags this reaction to the stable phenanthridinone products. This work provides a direct conversion of a broad range of 2-arylanilines to various phenanthridinones. This method could be applied in the synthesis of bioactive molecules and organic optoelectronic materials.

DMF as an amine source: iron-catalyzed cyclization of 2H-azirines to imidazoles

“…On the basis of the above experimental results and previous reports, 9–16,19 a plausible reaction mechanism is suggested in Scheme 7. First, in the presence of FeCl 2 , the cationic azirine complex A is formed.…”

“…9,10 Moreover, N , N -dimethylformamide (DMF) is not only one of the solvents with low price and easy access to raw materials, but also can be used as a multifunctional synthon to participate in various transformations. 11 Various heterocyclic compounds were synthesized by providing CH, 12 Me 2 NCO 13 and CO 14 units in these reactions (Scheme 1a). Meanwhile, DMF serving as the amine source (NMe 2 ) has been mainly applied in amination reaction (Scheme 1a).…”

EtOS2K as a C1 Source: Solvent- and Temperature-Controlled Selective Synthesis of Quinoline-2-thione and Quinoline-2-one Derivatives

“…Multiple methods to generate quinoline-2-one have been reported, and the C1 sources involved were CO, M­(CO) n , CO 2 , dioxazolones, and TFBen . Additionally, HCO 2 R, COCl 2 , DMF, etc . can also be derived as CO alternatives in specific reactions.…”

Synthesis Enabled by E-to-Z Isomerization Using CBZ6 as Energy Transfer Photocatalyst

“…The photocatalytic E → Z -isomerization of 1a has previously been reported using 3 mol % [Ir­(bpy)­(ppy) 2 ]­PF 6 as photocatalyst (PC) . In this work, the E → Z -isomerization of 1a was conducted using 1 mol % CBZ6 as a PC under 407 nm LEDs for 2 h. After removal of EtOAc under vacuum, the solvent CH 3 CN-DMSO (3 mL, 2/1 v/v) and t BuOK (1.5 mmol) were added, and the irradiation of 407 nm LEDs was maintained for 12 h. The method for the synthesis of 2a from ( Z )- 1a was modified from our previous reported base-promoted photochemical dehydrogenative C­(Ar)–H carbonylative lactamization of 2-arylanilines. − The transformation of 1a to 2a under the standard conditions gave a 90% yield (Table , entry 1). The E / Z ratio of the intermediate ( Z )- 1a was determined as 14/1.…”