Synlett, Inhaltsverzeichnis Synlett 2021; 32(07): 728-732DOI: 10.1055/a-1334-6450 letter Dirhodium-Catalyzed Chemo- and Site-Selective C–H Amidation of N,N-Dialkylanilines Authors Gong Chen Kenta Arai Kazuhiro Morisaki Takeo Kawabata Yoshihiro Ueda ∗ Artikel empfehlen Abstract Artikel einzeln kaufen(opens in new window) Alle Artikel dieser Rubrik(opens in new window) Abstract A method for dirhodium-catalyzed C(sp3)–H amidation of N,N-dimethylanilines was developed. Chemoselective C(sp3)–H amidation of N-methyl group proceeded exclusively in the presence of C(sp2)–H bonds of the electron-rich aromatic ring. Site-selective C(sp3)–H amidation proceeded exclusively at the N-methyl group of N-methyl-N-alkylaniline derivatives with secondary, tertiary, and benzylic C(sp3)–H bonds α to a nitrogen atom. Key words Key wordsC–H amidation - dirhodium complex - aniline - nitrene - site selectivity Volltext Referenzen References and Notes 1a Hartwig JF. Acc. Chem. 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ACS Cent. Sci. 2016; 2: 281 18b Shugrue CR, Miller SJ. Chem. Rev. 2017; 117: 11894 18c Hong B, Luo T, Lei X. ACS Cent. Sci. 2020; 6: 622 19 General Procedure for Dirhodium-Catalyzed C(sp3)–H Amidation of N,N-Dialkylanilines To a suspension of N,N-dialkylanilines (0.5 mmol, 10 equiv), TrocNHOTs (18.1 mg, 0.05 mmol, 1.0 equiv), and K2CO3 (10.4 mg, 0.075 mmol, 1.5 equiv) in toluene (0.25 mL) were added Rh2(oct)4 (1.9 mg, 0.05 equiv) at room temperature. After being stirred for 12 h, the reaction was quenched by addition of water and extracted with EtOAc. The organic layer was washed with brine and dried over Na2SO4, filtered, and concentrated. The yields of the aminated product 2 were determined by 1H NMR analysis using 1,3-dinitrobenzene as internal standard. The residue was purified by preparative TLC purification to afford the aminated product 2. Trichloroethyl{[methyl(phenyl)amino]methyl}carbamate (2aa) Colorless oil. 1H NMR (400 MHz, CDCl3, 323 K): δ = 7.29–7.25 (m, 2 H), 6.84–6.81 (m, 3 H), 5.41 (br s, 1 H), 4.91 (d, J = 6.0 Hz, 2 H), 4.73 (s, 2 H), 3.01 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 154.9, 147.7 129.6, 118.7, 113.6, 95.5, 74.6, 59.6, 37.8. IR (neat): 3326, 2952, 1722, 1598, 1499, 1367, 1220, 1132, 1041, 817, 750 cm–1. HRMS-ESI+: m/z calcd for C11H13Cl3N2O2 [M + H]+: 311.0115; found: 311.0115. Zusatzmaterial Zusatzmaterial Supporting Information (PDF)
