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Synlett 2020; 31(12): 1221-1225
DOI: 10.1055/s-0040-1707946
DOI: 10.1055/s-0040-1707946
letter
Cobalt-Catalyzed Decarboxylative Methylation and Ethylation of Aliphatic N-(Acyloxy)phthalimides with Organoaluminum Reagents
This work was supported by the National Natural Science Foundation of China (21901237) and KY (2060000019). G.-Z.W. thanks the China Postdoctoral Science Foundation (2018M640588).
Weitere Informationen
Publikationsverlauf
Received: 25. März 2020
Accepted after revision: 16. April 2020
Publikationsdatum:
05. Mai 2020 (online)
Abstract
A cobalt-catalyzed decarboxylative methylation of aliphatic redox-active esters [N-(acyloxy)phthalimides; RAEs] with trimethylaluminum under mild conditions was developed, providing a method for transforming a carboxylate group into a methyl group without redox fluctuation. Primary and secondary RAEs were both amenable substrates, whereas a tertiary RAE delivered an elimination product. Triethylaluminum was also used to deliver a decarboxylative ethylation product.
Key words
cobalt catalysis - decarboxylative methylation - ethylation - trimethylaluminum - redox-active estersSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707946.
- Supporting Information
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- 14 4-Methyl-1-tosylpiperidine (2); Typical Procedure Phthalimide 1 (1.0 equiv, 0.2 mmol), CoBr2 (10 mol%), and dpph (12 mol%) were placed in a 10 mL transparent Schlenk tube equipped with a stirring bar. The tube was evacuated and filled with argon three times. Anhyd DMF (2.0 mL) and a 2 M solution of AlMe3 in hexane (1.5 equiv) were added from a gastight syringe under argon, and the mixture was stirred at r.t. for 12 h. The reaction was then quenched with sat. aq sodium potassium tartrate solution, and the mixture was extracted with EtOAc (3 × 10 mL). The organic layers were combined and concentrated under vacuo. The crude product was purified by flash column chromatography [silica gel, EtOAc–PE (1:5)] to give a white solid; yield: 44.2 mg (88%); mp 83–85 °C. 1H NMR (400 MHz, CDCl3): d = 7.64 (d, J = 8.3 Hz, 2 H), 7.32 (d, J = 8.0 Hz, 2 H), 3.73 (d, J = 11.5 Hz, 2 H), 2.43 (s, 3 H), 2.22 (t, J = 10.9 Hz, 2 H), 1.67 (s, 2 H), 1.28 (dd, J = 12.4, 5.7 Hz, 3 H), 0.90 (d, J = 5.6 Hz, 3 H). 13C NMR (101 MHz, CDCl3): d = 143.2, 133.3, 129.5, 127.6, 46.3, 33.3, 30.1, 21.5, 21.4.