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Synlett 2023; 34(12): 1482-1486
DOI: 10.1055/a-1942-0683
DOI: 10.1055/a-1942-0683
cluster
Special Issue Honoring Masahiro Murakami’s Contributions to Science
Catalytic Generation of Radicals from Nitroalkanes
This work was supported by the Japan Society for the Promotion of Science (JSPS KAKENHI, Grant Numbers JP20H04814 in Hybrid Catalysis and 19J20969) and by the Toyo Gosei Memorial Foundation.
This paper is dedicated to Professor Masahiro Murakami on the occasion of his retirement.
Abstract
A new protocol for the catalytic denitrative generation of radicals from nitroalkanes was disclosed. 9-Fluorenol acts as a single-electron transfer catalyst that reduces nitroalkanes to promote the C-NO2 bond cleavage, followed by the formation of alkyl radicals. The obtained radicals participate in diverse transformations such as hydrogenation, Giese addition, spirocyclization, and Minisci reactions by using appropriate trapping reagents. The present system outperforms conventional methods using tin hydrides in terms of cost, toxicity, and experimental operations.
Key words
nitroalkane - 9-fluorenol - single-electron transfer - denitration - radical - organocatalysisSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1942-0683.
- Supporting Information
Publication History
Received: 12 August 2022
Accepted after revision: 13 September 2022
Accepted Manuscript online:
13 September 2022
Article published online:
19 October 2022
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- 29 Typical Procedure for the Denitrative Radical Transformation of Nitroalkanes A 15-mL vial equipped with a magnetic stirrer bar was charged with nitroalkane 1 (0.60 mmol), radical acceptor 2, 6, 8, or 10 (0.60–1.8 mmol), K3PO4 (0.90–1.8 mmol), and 2-propanol (3.0–6.0 mL) under a nitrogen atmosphere. The resulting mixture was stirred at 110 °C. After completion of the reaction, the mixture was filtered through a short pad of Celite® and eluted with EtOAc. All volatiles were removed in vacuo, and the residue was purified by a silica gel column chromatography. Analytical Data for 4l 1H NMR (400 MHz, acetone-d 6): δ = 7.36–7.19 (m, 5 H), 2.99 (dd, J = 14.2, 5.0 Hz, 1 H), 2.70 (dd, J = 14.0, 8.9 Hz, 1 H), 2.59–2.42 (m, 1 H), 1.65–1.45 (m, 2 H), 0.93 (td, J = 7.6, 0.9 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 138.6, 129.0, 128.5, 128.4 (q, J = 280.8 Hz), 126.5, 45.9 (q, J = 24.0 Hz), 33.7, 20.3, 11.2. 19F NMR (376 MHz, CDCl3): δ = –70.1. HRMS (EI) (+): m/z [M]+ calcd for C11H13F3: 202.0969; found: 202.0963. Analytical Data for 9e 1H NMR (400 MHz, acetone-d 6): δ = 7.39–7.33 (m, 2 H), 7.27–7.20 (m, 3 H), 7.11 (d, J = 10.2 Hz, 2 H), 6.46 (s, 1 H), 6.19 (d, J = 10.1 Hz, 2 H), 2.16 (s, 2 H), 1.74–1.58 (m, 6 H), 1.57–1.36 (m, 4 H). 13C NMR (101 MHz, CDCl3): δ = 185.9, 156.4, 140.7, 140.6, 135.3, 128.3, 127.9, 127.8, 125.9, 56.0, 48.7, 48.6, 38.8, 25.6, 23.3. ESI-HRMS (+): m/z [M + Na]+ calcd for C21H22ONa: 313.1563; found: 313.1561. Experimental details and analytical data for other compounds are provided in the Supporting Information.