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Synlett 2022; 33(18): 1826-1830
DOI: 10.1055/a-1770-1078
DOI: 10.1055/a-1770-1078
cluster
Development and Applications of Novel Ligands/Catalysts and Mechanistic Studies on
Catalysis
Palladium-Catalyzed Coupling of Biphenyl-2-yl Trifluoromethanesulfonates with Dibromomethane to Access Fluorenes
Authors
The work was supported by the National Natural Science Foundation of China (No. 21971196) and the Science and Technology Commission of Shanghai Municipality (19DZ2271500).
Abstract
A facile and efficient method has been developed for the synthesis of fluorenes by Pd-catalyzed C–H alkylation of biphenyl-2-yl trifluoromethanesulfonates. The trifluoromethanesulfonates are more readily available and more environmentally benign than biphenyl iodides, and are advantageous substrates for traceless directing-group-assisted C–H activation. The reaction generates C,C-palladacycles as the key intermediates that form two C(sp2)–C(sp3) bonds through reaction with CH2Br2. The reaction tolerates various functional groups, permitting easy access to a range of fluorene derivatives.
Key words
palladium catalysis - fluorenes - C–H bond activation - biphenyl triflates - dibromomethaneSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1770-1078.
- Supporting Information (PDF)
Publication History
Received: 16 January 2022
Accepted after revision: 11 February 2022
Accepted Manuscript online:
11 February 2022
Article published online:
10 March 2022
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- 14 Fluorenes 3; General Procedure A 25 mL Schlenk tube equipped with a stirrer bar was charged with the appropriate biphenyl-2-yl triflate 1 (0.2 mmol, 1.0 equiv), CH2Br2 (1.4 mmol, 7.0 equiv), Pd(OAc)2 (0.02 mmol, 0.1 equiv), KHCO3 (0.4 mmol, 2.0 equiv), KOAc (0.6 mmol, 3.0 equiv), i-PrOH (0.2 mL), and DMF (2.0 mL). The tube was then frozen with liquid N2 and exchanged with N2 to remove air. The mixture was then stirred at 60 °C for 12 h until the reaction was complete. The resulting mixture was diluted with EtOAc and washed with sat. aq NaCl (3×). The organic phase was collected and dried (MgSO4), and the residue was purified by column chromatography (silica gel, petroleum ether/EtOAc). 9H-Fluorene (3a) White solid (80%). 1H NMR (400 MHz, CDCl3): δ = 7.81 (d, J = 7.5 Hz, 2 H), 7.56 (d, J = 7.4 Hz, 2 H), 7.39 (t, J = 7.3 Hz, 2 H), 7.32 (td, J = 7.3, 0.9 Hz, 2 H), 3.92 (s, 2 H). 13C NMR (101 MHz, CDCl3): δ = 143.2, 141.7, 126.7, 126.7, 125.0, 119.8, 36.9. HRMS (ESI-TOF): m/z [M + H]+ calcd for C13H11: 167.0855; found: 167.0865. 2-Methyl-9H-fluorene (3b) White solid (56%). 1H NMR (400 MHz, CDCl3): δ = 7.76 (d, J = 7.5 Hz, 1 H), 7.68 (d, J = 7.7 Hz, 1 H), 7.53 (d, J = 7.4 Hz, 1 H), 7.39–7.35 (m, 2 H), 7.31–7.25 (m, 1 H), 7.20 (d, J = 7.7 Hz, 1 H), 3.87 (s, 2 H), 2.44 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 143.5, 143.0, 141.8, 139.0, 136.5, 127.5, 126.6, 126.2, 125.7, 124.9, 119.6, 119.5, 36.8, 21.6. HRMS (ESI-TOF): m/z [M – H]+ calcd for C14H11: 179.0855; found: 179.0866. 3-Methyl-9H-fluorene (3c) White solid (70%). 1H NMR (400 MHz, CDCl3): δ = 7.78 (d, J = 7.5 Hz, 1 H), 7.62 (s, 1 H), 7.54 (d, J = 7.4 Hz, 1 H), 7.44 (d, J = 7.6 Hz, 1 H), 7.38 (t, J = 7.4 Hz, 1 H), 7.34–7.27 (m, 1 H), 7.14 (d, J = 7.6 Hz, 1 H), 3.87 (s, 2 H), 2.47 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 143.6, 141.8, 141.7, 140.3, 136.3, 127.6, 126.6, 126.5, 125.0, 124.7, 120.4, 119.70, 36.5, 21.5. HRMS (ESI-TOF): m/z [M – H]+ calcd for C14H11: 179.0855; found: 179.0873. 4-Methyl-9H-fluorene (3d) White solid (44%). 1H NMR (400 MHz, CDCl3): δ = 7.94 (d, J = 7.7 Hz, 1 H), 7.58 (d, J = 7.4 Hz, 1 H), 7.40 (t, J = 7.9 Hz, 2 H), 7.32 (td, J = 7.4, 0.7 Hz, 1 H), 7.22 (t, J = 7.4 Hz, 1 H), 7.16 (d, J = 7.4 Hz, 1 H), 3.92 (s, 2 H), 2.74 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 143.6, 143.6, 142.7, 139.8, 133.0, 129.0, 126.6, 126.4, 126.0, 124.9, 123.1, 122.4, 37.1, 21.1. HRMS (ESI-TOF): m/z [M – H]+ calcd for C14H11: 179.0855; found: 179.0880.
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