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Synlett 2024; 35(08): 903-907
DOI: 10.1055/a-2268-4678
DOI: 10.1055/a-2268-4678
cluster
Special Issue dedicated to Keith Fagnou
Manganese(I)-Catalyzed C–H Allylation of Tryptophans and Their Oligopeptides On Water
Generous support from the Deutsches Zentrum für Herz-Kreislaufforschung (DZHK) (PI at the German Centre for Cardiovascular Research), the European Research Council (ERC) (Advanced Grant 101021358), and the DFG (Gottfried-Wilhelm-Leibniz Prize) to L.A. are gratefully acknowledged. We are also grateful for support from the European Union’s Horizon 2020 research and innovation program, H2020 Marie Skłodowska-Curie Actions (Grant Agreement No. 860762) to T.O., and warmly acknowledge Novartis for financial support.
Abstract
The manganese(I)-catalyzed allylation of the amino acid tryptophan is realized under exceedingly mild conditions using water as a sustainable and non-hazardous reaction medium, instead of classical organic solvents, with great potential for green and sustainable chemistry. Synthetically useful α,β-unsaturated esters can be accessed by reaction with Morita–Baylis–Hillman (MBH) adducts following a fast C–H activation approach. The robustness of this procedure is reflected by kinetic analysis at different reaction temperatures and reduced catalyst loadings are employed.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2268-4678.
- Supporting Information
Publication History
Received: 21 January 2024
Accepted after revision: 14 February 2024
Accepted Manuscript online:
14 February 2024
Article published online:
27 February 2024
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- 67 Butyl ((S)-2-((3-(2-((tert-Butoxycarbonyl)amino)-3-methoxy-3-oxopropyl)-1-(pyridin-2-yl)-1H-indol-2-yl)methyl)acrylate) (3a); Typical Procedure Tryptophan 1 (63.4 mg, 0.20 mmol, 1.00 equiv), MnBr(CO)5 (5.5 mg, 20 μmol, 10 mol%) and NaOAc (4.9 mg, 60 μmol, 30 mol%) were placed in a 10 mL vial. The vial was then evacuated and filled with N2 three times. Afterwards, the MBH adduct 2a (103 mg, 0.40 mmol, 2.00 equiv) and freshly degassed H2O (1.5 mL) were added and the suspension was stirred at 80 °C for 16 h under N2. After cooling to ambient temperature, EtOAc (10 mL) was added, the organic phase was separated, and the aqueous phase was extracted with EtOAc (3 × 10 mL). After drying of the combined organic phases over Na2SO4, the crude mixture was concentrated in vacuo. Purification by column chromatography (SiO2, n-hexane/EtOAc = 4:1) afforded the desired product 3a (91.1 mg, 85%) as a colorless oil. 1H NMR (400 MHz, CDCl3): δ = 8.57 (d, J = 4.6 Hz, 1 H), 7.82 (dt, J = 7.8, 1.5 Hz, 1 H), 7.57 (dd, J = 3.9, 3.9 Hz, 1 H), 7.38–7.22 (m, 3 H), 7.19–7.09 (m, 2 H), 5.97 (d, J = 2.0 Hz, 1 H), 5.18 (d, J = 8.1 Hz, 1 H), 5.02 (d, J = 2.2 Hz, 1 H), 4.65 (q, J = 6.6 Hz, 1 H), 4.07 (td, J = 6.7, 1.3 Hz, 2 H), 3.96 (s, 2 H), 3.66 (d, J = 1.3 Hz, 3 H), 3.30 (d, J = 5.1 Hz, 2 H), 1.58 (q, J = 6.9 Hz, 2 H), 1.40 (s, 9 H), 1.35–1.27 (m, 2 H), 0.90 (t, J = 7.4 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 172.9 (Cq), 166.5 (Cq), 155.3 (Cq), 151.4 (Cq), 149.6 (CH), 138.4 (CH), 137.8 (Cq), 136.9 (Cq), 134.6 (Cq), 128.7 (Cq), 126.0 (Cq), 122.6 (CH), 122.2 (CH), 121.0 (CH), 120.8 (CH), 118.8 (CH), 110.7 (CH2), 110.3 (CH), 79.8 (Cq), 64.8 (CH2), 62.6 (CH2), 54.1 (CH), 52.4 (CH3), 30.7 (CH2), 28.4 (CH3), 27.0 (CH2), 19.2 (CH2), 13.8 (CH3). HRMS (ESI): m/z [M + Na]+ calcd for C30H37N3O6Na: 558.2575; found: 558.2575.
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