Synlett 2021; 32(04): 391-394
DOI: 10.1055/s-0040-1707295
cluster
Radicals – by Young Chinese Organic Chemists

Synthesis of Chiral Fluorides by Sequential Organocatalyzed Desymmetrization of Glutaric Anhydrides and Photoredox-Catalyzed Decarboxylic Fluorination

Jia-Jia Zhao
,
Shouyun Yu
State Key Laboratory of Analytical Chemistry for Life Science, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, P. R. of China   Email: yushouyun@nju.edu.cn
› Author Affiliations
Financial support from National Natural Science Foundation of China (21732003) is acknowledged.


Abstract

We have developed an efficient method for the preparation of chiral fluorinated compounds by sequential organocatalyzed desymmetrization of 3-substituted glutaric anhydrides and photoredox-catalyzed decarboxylic fluorination. Chiral fluorides can be prepared in yields of up to 58% and with excellent enantioselectivities of up to 98% ee.

Supporting Information



Publication History

Received: 30 June 2020

Accepted after revision: 26 August 2020

Publication Date:
22 September 2020 (online)

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  • 12 Alkyl 3-Aryl-4-fluorobutanoates 3; General Procedure MTBE (15 mL) was added to a mixture of the appropriate 3-arylglutaric anhydride 1 (0.5 mmol) and catalyst A4 (0.05 mmol), and the mixture was stirred at –20 °C for 30 min. MeOH (5 mmol) was added, and stirring was continued at –20 °C for 24 h. When the reaction was complete, the solvent was evaporated under reduced pressure without further purification. The residue was dissolved in 1:1 MeCN–H2O (5.0 mL) and Ir(ppy)2(dtbbpy)PF6 (I) (0.010 mmol, 2 mol%), Selectfluor (1.5 mmol), and Na2HPO4 (1 mmol) were added. The mixture was irradiated by 40 W (456 nm) blue LEDs for 12 h at 25 °C under N2 until the reaction was complete. The reaction was then quenched with aq NaCl, the mixture was extracted with Et2O, and the extracts were purified by preparative TLC.
  • 13 Methyl (R)-4-Fluoro-3-phenylbutanoate (3a) Purified by preparative TLC (PE–EtOAc, 10:1) to give a white oil; yield: 56.8 mg (58%, ee 92%); [α]D 20 = –37.9 (c 2.15, CHCl3). HPLC [Daicel Chiralpak OD-H, hexane–i-PrOH (98:2), flow rate: 1.0 mL/min, T = 25 °C, λ = 220 nm]: t R = 8.292 min (major), t R = 14.765 min (minor). 1H NMR (400 MHz, CDCl3): δ = 7.36–7.29 (m, 2 H), 7.28–7.22 (m, 3 H), 4.68–4.41 (m, 2 H), 3.62 (s, 3 H), 3.59–3.46 (m, 1 H), 2.89 (dd, J = 16.0, 6.9 Hz, 1 H), 2.70 (dd, J = 16.0, 8.0 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 172.2, 139.5, 128.7, 127.8, 127.4, 86.1 (J = 173.0 Hz), 51.7, 42.6, 36.3. 19F NMR (376 MHz, CDCl3): δ = –219.8. ESI (FTMS): m/z [M + Na]+ calcd for C11H13FNaO2: 219.0798; found: 219.0801.