Copper-catalyzed one-pot three-component thioamination of 1,4-naphthoquinone

Abstract

A concise one-pot three-component thioamination of 1,4-naphthoquinone with thiols and amines was developed to synthesize 2-amino-3-thio-1,4-naphthoquinones.

Silver-Catalyzed One-Pot Biarylamination of Quinones with Arylamines: Access to N-Arylamine-Functionalized p-Iminoquinone Derivatives

“…10 In 2019, Chen and co-workers developed a copper-catalyzed one-pot three-component thioamination of quinones with amines and thiols (Scheme 1b). 11 Very recently, in 2021, Wang and co-workers reported a copper-catalyzed one-pot amine-alkylation of quinones with amines and alkanes with DTBP for the first time. 12 From the above reports, it can be seen that one-pot difunctionalization of quinones is rare.…”

Metal‐Free, PhI(OAc)2‐Promoted Oxidative C(sp2)−H Difunctionalization: Synthesis of Thioaminated Naphthoquinones

“…After evaporation the residue was purified by column chromatography on silica gel to obtain the desired products (eluent: ethyl acetate/petroleum ether). [39] Yield: 80%, 279 mg; red solid; mp 56. [39] Yield: 62%, 226 mg; red solid; mp 53.5-55 °C; R f = 0.45 (EA: PE = 10: 90); 1 [39] Yield: 73%, 254 mg; red solid; mp 72-73.9 °C; R f = 0.5 (EA: PE = 8: 92); 1 [39] Yield: 72%, 245 mg; red solid; mp 48.6-49.8 °C; R f = 0.5 (EA: PE = 4: 96); 1 H NMR (CDCl 3, 400 MHz): δ 8.07-8.04 (m, 1H), 7.87-7.84 (m, 1H), 7.66-7.62 (m, 1H), 7.57-7.53 (m, 1H), 3.91-3.88 (m, 4H), 2.88-2.82 (m, 1H), 1.94-1.90 (m, 4H), 1.87-1.83 (m,2H), 1.72-1.69 (m,2H), 1.57-1.53 (m,1H), 1.28-1.17(m, 5H); 13 [39] Yield: 67%, 255 mg; red solid; mp 149.0-150.0 °C; R f = 0.45 (EA: PE = 8: 92); 1 [39] Yield: 66%, 250 mg; red solid; mp 79.2-80.2 °C; R f = 0.5 (EA: PE = 6: 94); 1…”

“…[38] Very recently, a copper-catalyzed one-pot three-component reaction for thioamination of 1,4-naphthoquinone has been reported using molecular oxygen as an oxidant. [39] For few years, our research group are engaged in developing several environmentally benign methodologies using the organocatalysts. [40][41][42][43] Presently, iodine(III) reagents including phenyliodonium(III) diacetate (PIDA) have been raised as an alternative to transition-metal catalysts.…”

Metal-/catalyst-free one-pot three-component thioamination of 1,4-naphthoquinone in a sustainable solvent

“…In 2019, our group realized CuI-catalyzed one-pot thioamination of 1,4-naphthoquinone under 100 1C and an oxygen atmosphere using N,N-dimethylformamide (DMF) as a solvent. 13 However, this reaction still required harsh conditions in the conventional toxic organic solvent. In our continuing commitment to sustainable chemistry, we herein would like to disclose a catalystfree one-pot three-component thioamination strategy in a green solvent to synthesize 2-amino-3-thio-1,4-naphthoquinones (Scheme 1b).…”