Synlett 2018; 29(14): 1851-1856
DOI: 10.1055/s-0036-1591601
letter
© Georg Thieme Verlag Stuttgart · New York

A Synthetic Strategy for 2-Alkylchromanones: Fe(III)-Catalyzed ­Reductive Cross-Coupling of Unactivated Alkenes with Chromones

Xu-Ling Chen
a   Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China   Email: Jiyuwang@cioc.ac.cn
b   University of Chinese Academy of Sciences, Beijing 100049, P. R. of China
,
Yu Dong
a   Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China   Email: Jiyuwang@cioc.ac.cn
b   University of Chinese Academy of Sciences, Beijing 100049, P. R. of China
,
Lei Tang
c   Laboratory of Anaesthesia & Critical Care Medicine, Translational Neuroscience Center, and Department of Anaesthesiology, West China Hospital, Sichuan University, Chengdu 610041, P. R. of China
,
Xiao-Mei Zhang
a   Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China   Email: Jiyuwang@cioc.ac.cn
,
Ji-Yu Wang*
a   Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China   Email: Jiyuwang@cioc.ac.cn
› Author Affiliations
This work is supported by Science and Technology Department of ­Sichuan Province under grant number 2015JY0171.
Further Information

Publication History

Received: 30 April 2018

Accepted after revision: 08 June 2018

Publication Date:
10 July 2018 (online)


Abstract

A new synthetic approach for 2-alkylchromanones utilizing Fe (III)-catalyzed reductive cross-coupling of olefins with chromones has been developed. The reaction conditions are mild, and various substituted alkenes are applicable to the process. Moreover, control experiments were conducted, and a plausible mechanism is proposed.

Supporting Information

 
  • References and Notes

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  • 13 Experimental Procedure and Characterization Data for Compound 3af To a solution of chromone 1a (0.3 mmol, 1 equiv) and Fe(acac)3 (31.8 mg, 0.09 mmol, 30 mol%) in EtOH (1.5 mL, 0.2 M) were added olefin 2f (0.9 mmol, 3 equiv) and PhSiH3 (74 μL, 0.9 mmol, 3 equiv). The resulting mixture was heated in an oil bath preheated to 40 °C with stirring for 5 h. The reaction mixture was then cooled to room temperature, diluted with brine, and extracted with EtOAc (3 × 5 mL). The combined organic layers were washed with brine, dried with Na2SO4, filtered, and concentrated under reduced pressure. The resulting crude product was then purified by column chromatography on silica gel (petroleum ether/EtOAc = 5:1) to afford the desired product 3af as a colorless oil (58.3 mg, 83% yield). 1H NMR (300 MHz, CDCl3): δ = 7.83 (dt, J = 7.5, 0.5 Hz, 1 H), 7.46–7.41 (m, 1 H), 7.0–6.94 (m, 2 H), 4.14 (dd, J = 12.9, 3.6 Hz, 1 H), 3.80–3.75 (m, 2 H), 2.77–2.61 (m, 2 H), 1.94 (s, 1 H), 1.80–1.77 (m, 1 H), 1.71–1.23 (m, 1 H), 1.06 (d, J = 4.8 Hz, 6 H) ppm. 13C NMR (75 Hz, CDCl3): δ = 193.33, 161.80, 135.91, 126.84, 121.18, 120.72, 117.73, 84.23, 59.06, 40.95, 38.05, 36.11, 23.38, 23.12 ppm. HRMS (ESI): m/z [M + H]+ calcd for C14H19O3 +: 235.1328; found: 235.1327.
  • 14 Experimental Procedure for Compound 3if on Gram Scale To a solution of substrate 1i (1.36 g, 8 mmol, 1 equiv) and Fe(acac)3 (0.84 g, 2.4 mmol, 30 mol%) in EtOH (40 mL, 0.2 M) were added olefin 2f (24 mmol, 3 equiv) and PhSiH3 (2 mL, 24 mmol, 3 equiv). The resulting mixture was heated in an oil bath preheated to 40 °C with stirring for 5 h. The reaction mixture was then cooled to room temperature, diluted with brine, and extracted with EtOAc (3 × 20 mL). The combined organic layers were washed with brine, dried with Na2SO4, filtered, and concentrated under reduced pressure. The resulting crude product was then purified by column chromatography on silica gel (petroleum ether/EtOAc = 3:1) to afford the desired product 3if as a slightly yellow solid (1.51 g, 73% yield).