Synlett 2017; 28(18): 2421-2424
DOI: 10.1055/s-0036-1588474
cluster
© Georg Thieme Verlag Stuttgart · New York

A Borane-Catalyzed Metal-Free Hydrosilylation of Chromones and Flavones

Xiaoyu Rena, b, Caifang Hana, b, c, Xiangqing Fenga, b, Haifeng Du*a, b
  • aBeijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. of China   Email: haifengdu@iccas.ac.cn
  • bUniversity of Chinese Academy of Sciences, Beijing 100049, P. R. of China
  • cCollege of Chemistry and Material Sciences, Hebei Normal University, Shijiazhuang, Hebei 050024, P. R. of China
We are grateful for the generous financial support by the National Natural Science Foundation of China (21222207, 21572231, 21521002).
Further Information

Publication History

Received: 28 April 2017

Accepted after revision: 29 May 2017

Publication Date:
06 July 2017 (eFirst)

Published as part of the Cluster Silicon in Synthesis and Catalysis

Abstract

A Piers-type hydrosilylation of chromones and flavones has been successfully realized for the first time using 0.1 mol % of borane catalyst generated in situ by hydroboration of pentafluorostyrene with HB(C6F5)2 to afford a variety of chromanones and flavanones in 60–99% yields. An attempt for the asymmetric transformation with chiral diyne and HB(C6F5)2 gave chromanones and flavanones in high yields with up to 32% ee.

Supporting Information

 
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  • 17 General Procedure for Hydrosilylations To a tube, HB(C6F5)2 (0.0035 g, 0.01 mmol), 2,3,4,5,6-pentafluorostyrene (0.0019 g, 0.01 mmol), and dry toluene (0.10 mL) were added in a nitrogen atmosphere glovebox. The resulting mixture was stirred for 5 min at r.t. to afford a catalyst solution (0.10 M). To a sealing tube (15 mL), catalyst solution (0.0004 mmol, 4 μL, 0.1 M), PhMe2SiH (0.0649 g, 0.48 mmol), chromone or flavone 1(0.0644 g, 0.4 mmol), and dry toluene (0.8 mL) were added. The reaction mixture was stirred at 80 °C for 15 h, and then was cooled to r.t. followed by addition of TFA (0.0547 g, 0.48 mmol). The resulting mixture stirred at r.t. for 10 min and was concentrated and purified by column chromatography on silica gel to afford the corresponding products 3. 2-Isopropylchroman-4-one (3d) Colorless oil, 0.0593 g, 78% yield. 1H NMR (400 MHz, CDCl3): δ = 7.87 (d, J = 7.6 Hz, 1 H), 7.46 (dd, J = 8.0, 7.6 Hz, 1 H), 6.99 (m, 2 H), 4.21–4.16 (m, 1 H), 2.75–2.62 (m, 2 H), 2.12–2.18 (m, 1 H), 1.08 (d, J = 6.8 Hz, 3 H), 1.05 (t, J = 6.8 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 193.1, 162.0, 136.0, 127.0, 121.1, 121.0, 118.0, 82.6, 40.1, 32.2, 17.92, 17.90 ppm. 2-(2-Fluorophenyl)chroman-4-one (3i) Light yellow oil, 0.0582 g, 60% yield. 1H NMR (400 MHz, CDCl3): δ = 7.95 (d, J = 7.6 Hz, 1 H), 7.64 (dd, J = 7.6, 7.6 Hz, 1 H), 7.52 (dd, J = 8.6, 8.0 Hz, 1 H), 7.40–7.32 (m, 1 H), 7.27–7.20 (m, 1 H), 7.14–7.04 (m, 3 H), 5.79 (dd, J = 13.2, 2.8 Hz, 1 H), 3.06 (dd, J = 16.8, 13.2 Hz, 1 H), 2.93 (dd, J = 16.8, 3.2 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 191.6, 161.6, 159.7 (d, JC–F = 246.0 Hz), 136.3, 130.3 (d, JC–F = 9.0 Hz), 127.6 (d, JC–F = 4.0 Hz), 127.2, 126.3 (d, JC–F = 13.0 Hz), 124.7 (d, JC–F = 3.0 Hz), 121.9, 121.0, 118.2, 115.8 (d, JC–F = 21.0 Hz), 73.9 (d, JC–F = 3.0 Hz), 43.8 ppm.19F NMR (470 MHz, CDCl3): δ = –121.8 ppm.