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Synlett 2017; 28(16): 2163-2168
DOI: 10.1055/s-0036-1590805
DOI: 10.1055/s-0036-1590805
letter
Copper-Catalyzed Cleavage of Unstrained C–C Bonds for the Synthesis of 1-Acyloxy-2,2,6,6-tetramethylpiperidines from Cyclic or Acyclic Ketones
Financial support from National Science Foundation of China (No. 21372188), Hunan Provincial Natural Science Foundation (14JJ6012), and the State Key Laboratory of Natural and Biomimetic Drugs are greatly appreciated.Further Information
Publication History
Received: 17 April 2017
Accepted after revision: 22 May 2017
Publication Date:
13 July 2017 (online)
![](https://www.thieme-connect.de/media/synlett/201716/lookinside/thumbnails/st-2017-w0266-l_10-1055_s-0036-1590805-1.jpg)
Abstract
A copper-catalyzed approach for the synthesis of 1-acyloxy-2,2,6,6-tetramethylpiperidines through the C–C bond cleavage of cyclic or acyclic ketones was developed. In this chemistry, a combination of CuCl2·2H2O, 1,10-phenanthroline monohydrate, and aniline was crucial for the formation of the desired products by the reaction of ketones with TEMPO. This research provides a new strategy for the further transformation of α-aryl cyclic or acyclic ketones.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590805.
- Supporting Information
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- 12 2-{3-Oxo-3-[(2,2,6,6-tetramethylpiperidin-1-yl)oxy]propyl}benzaldehyde (3aa); Typical Procedure A tube equipped with a condenser was successively charged with 2-tetralone (1a, 0.5 mmol, 73.1 mg), TEMPO (2a, 0.25 mmol, 39.1 mg), CuCl2·2 H2O (0.025 mmol, 4.3 mg), 1,10-phenanthroline monohydrate (0.05 mmol, 9.9 mg), aniline (0.025 mmol, 2.3 mg, 2.3 μL), and MeCN (2 mL), and the mixture was stirred at 40 °C under air. When the reaction was complete (TLC), the mixture was cooled to r.t., dried under vacuum, and purified by column chromatography [silica gel, PE–EtOAc (5:1)] to give a solid; yield: 74 mg (93%); mp 56–57 °C. 1H NMR (400 MHz, CDCl3): δ = 10.23 (s, 1 H), 7.81 (d, J =7.6 Hz, 1 H), 7.50 (t, J = 7.4 Hz, 1 H), 7.44–7.36 (m, 2 H), 3.41 (t, J = 7.6 Hz, 2 H), 2.69 (t, J = 7.6 Hz, 2 H), 1.72–1.35 (m, 6 H), 1.09 (s, 6 H), 0.95 (s, 6 H); 13C NMR (100 MHz, CDCl3): δ = 192.7, 172.3, 142.7, 133.8, 133.7, 133.6, 131.5, 127.0, 59.8, 38.8, 34.0, 31.8, 28.2, 20.4, 16.9.
For selected reviews on cleavage of unstrained C–C bonds, see:
For selected recent examples on cleavage of C–C bonds of unstrained ketones or aldehydes, see:
For some recent reviews on metal-catalyzed aerobic oxidation, see: