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Synlett 2021; 32(07): 728-732
DOI: 10.1055/a-1334-6450
DOI: 10.1055/a-1334-6450
letter
Dirhodium-Catalyzed Chemo- and Site-Selective C–H Amidation of N,N-Dialkylanilines
This research was financially supported by Grants-in-Aids for Scientific Research S (JP26221301) and Scientific Research C (JP20K06964) from the Japan Society for the Promotion of Science. Y.U. acknowledges the financial support from the Uehara Memorial Foundation. G.C. acknowledges the China Scholarship Council for the financial support.
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.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1334-6450.
- Supporting Information
Publication History
Received: 16 November 2020
Accepted after revision: 10 December 2020
Accepted Manuscript online:
10 December 2020
Article published online:
07 January 2021
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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.
C(sp3)–H amidation by Cu catalysis:
C(sp3)–H amidation by Fe catalysis:
C(sp3)–H amidation under transition-metal-free conditions:
C(sp3)–H amidation with hypervalent iodine reagents or N-haloimide reagents:
Cu-nitrene-mediated C(sp3)–H amidation of N-methylaniline derivatives has been reported, see:
For selected pioneering examples, see: