Copper-Catalyzed Cleavage of Unstrained C–C Bonds for the Synthesis of 1-Acyloxy-2,2,6,6-tetramethylpiperidines from Cyclic or Acyclic Ketones

Qijian Jiang; Luo Yang; Wang Zhou

doi:10.1055/s-0036-1590805

Synlett, Table of Contents

Synlett 2017; 28(16): 2163-2168
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

Authors

Qijian Jiang

^aCollege of Chemical Engineering, Xiangtan University, Xiangtan 411105, P. R. of China
Luo Yang

^cCollege of Chemistry, Xiangtan University, Xiangtan 411105, P. R. of China Email: wzhou@xtu.edu.cn
Wang Zhou *

^aCollege of Chemical Engineering, Xiangtan University, Xiangtan 411105, P. R. of China

^bState Key Laboratory of Natural and Biomimetic Drugs, Peking University, Xue Yuan Road 38, Beijing 100191, P. R. of China

Abstract

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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.

Key words

copper catalysis - acyloxypiperidines - C–C bond cleavage - ketones - TEMPO

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References

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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.

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Supplementary Material

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