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Synlett
DOI: 10.1055/a-2341-9274
DOI: 10.1055/a-2341-9274
letter
Efficient Synthesis of Fluorene Derivatives by Benzannulation of Indene Dienes with Benzoylacetonitrile Catalyzed by Lipase
We gratefully acknowledge the Science and Technology Development Program of Jilin Province (No. YDZJ202201ZYTS102).
Abstract
An enzymatic method was developed for the synthesis of fluorene derivatives by benzannulation of indene dienes with benzoylacetonitrile in a nonaqueous solvent. Under the optimal reaction condition [indene diene (0.5 mmol), benzoylacetonitrile (0.5 mmol), ethanol (2 mL), lipase from porcine pancreas (5 mg), 50 °C, 24 h], fluorenes bearing various groups were obtained in satisfactory yields (83–93%). This method not only offers a significant advancement in the synthesis of fluorene derivatives, but also represents a new application of lipase in promiscuous enzyme catalysis.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2341-9274.
- Supporting Information
Publication History
Received: 28 May 2024
Accepted after revision: 10 June 2024
Accepted Manuscript online:
10 June 2024
Article published online:
12 July 2024
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- 44 Fluorene Derivatives 3a–k; General Procedure The appropriate indene diene 1 (0.5 mmol), benzoylacetonitrile (2; 0.5 mmol), and PPL (5 mg) were added to EtOH (2 mL), and the mixture was stirred at 50 °C in a shaker until the reaction was complete (TLC). The product was then purified by flash column chromatography [silica gel, PE–EtOAc (2:1 to 10:1)]. 3-Amino-1-phenyl-9H-fluorene-2,4-dicarbonitrile (3a) Fluorescent solid; yield: 93%. 1H NMR (400 MHz, DMSO-d6): δ = 3.72 (s, 2 H), 6.78 (s, 2 H), 7.53–7.60 (m, 8 H), 8.28 (d, J = 7.56 Hz, 1 H). 3-Amino-1-(3-methylphenyl)-9H-fluorene-2,4-dicarbonitrile (3b) Fluorescent solid; yield: 86%. 1H NMR (400 MHz, DMSO-d6): δ = 3.72 2.42 (s, 3 H), 3.71 (s, 2 H), 6.75 (s, 2 H), 7.34–7.74 (m, 6 H), 8.42 (d, J = 8.08 Hz, 2 H). The NMR spectra of the products were identical to those previously reported.19