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Synlett 2020; 31(10): 997-1002
DOI: 10.1055/s-0040-1707991
DOI: 10.1055/s-0040-1707991
letter
Lanthanum(III) Trifluoromethanesulfonate Catalyzed Direct Synthesis of Ureas from N-Benzyloxycarbonyl-, N-Allyloxycarbonyl-, and N-2,2,2-Trichloroethoxycarbonyl-Protected Amines
This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2018R1D1A1B07047572).Further Information
Publication History
Received: 09 January 2020
Accepted after revision: 16 February 2020
Publication Date:
06 March 2020 (online)
Abstract
A novel lanthanum triflate mediated conversion of N-benzyloxycarbonyl-, N-allyloxycarbonyl-, and N-trichloroethoxycarbonyl-protected amines into nonsymmetric ureas was discovered. In this study, lanthanum triflate was found to be an effective catalyst for preparing various nonsymmetric ureas from protected amines. A variety of protected aromatic and aliphatic carbamates reacted readily with various amines in the presence of lanthanum triflate to generate the desired ureas in high yields. This result demonstrated that this novel lanthanum triflate catalyzed preparation of ureas from Cbz, Alloc, and Troc carbamates can be employed for the formation of various urea structures.
Key words
ureas - amines - lanthanum triflate catalysis - benzyloxycarbonyl amines - allyloxycarbonyl amines - trichloroethoxycarbonyl aminesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707991.
- Supporting Information
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N-Butyl-N′-phenylurea (3a); Typical ProcedureButylamine (2a; 0.110 g, 1.5 mmol) was added dropwise to a solution of N-Cbz-aniline (1a; 0.177 g, 1.00 mmol) and La(OTf)3 (0.088 g, 0.15 mmol) in PhCF3 (2 mL) at r.t., and the mixture was stirred and heated to 70 °C for 12 h under N2. The mixture was then cooled to r.t. and 1 M aq HCl (10 mL) was added. The resulting mixture was extracted with CH2Cl2 (2 × 20 mL), and the combined organic layers were dried (Na2SO4) and concentrated under reduced pressure. The resulting residue was purified by flash column chromatography (silica gel, 0–50% hexane–EtOAc) to give a white solid; yield: 0.180 g (94%); mp 129–131 °C.1H NMR (400 MHz, DMSO-d
6): δ = 8.35 (s, 1 H), 7.39–7.36 (m, 2 H), 7.22–7.18 (m, 2 H), 6.89 (t, J = 7.2 Hz, 1 H), 6.08 (t, J = 5.2 Hz, 1 H), 3.08 (q, J = 6.0 Hz, 2 H), 1.45–1.38 (m, 2 H), 1.34–1.24 (m, 2 H), 0.89 (t, J = 7.2 Hz, 3 H). 13C NMR (100 MHz, DMSO-d
6): δ = 155.64, 141.06, 129.05 (2 C), 112.31, 111.7 (2 C), 39.13, 32.35, 19.99, 14.16. HRMS (ESI): m/z [M + H]+ calcd for C11H17N2O: 193.1341; found: 193.1336.