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Synlett 2017; 28(16): 2194-2198
DOI: 10.1055/s-0036-1588475
letter
© Georg Thieme Verlag Stuttgart · New York

A Highly Efficient Gold(I)-Catalyzed Mukaiyama–Mannich Reaction of α-Amino Sulfones with Fluorinated Silyl Enol Ethers To Give β-Amino α-Fluorinated Ketones

Xiao-Si Hu
a   Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, 3663N Zhongshan Road, Shanghai 200062, P. R. of China   Email: jzhou@chem.ecnu.edu.cn
,
Yi Du
b   Xinhua Hospital, affiliated to Shanghai Jiaotong University School of Medicine, Shanghai, Shanghai 200032, P. R. of China
,
Jin-Sheng Yu*
a   Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, 3663N Zhongshan Road, Shanghai 200062, P. R. of China   Email: jzhou@chem.ecnu.edu.cn
,
Fu-Min Liao
a   Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, 3663N Zhongshan Road, Shanghai 200062, P. R. of China   Email: jzhou@chem.ecnu.edu.cn
,
Pei-Gang Ding
a   Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, 3663N Zhongshan Road, Shanghai 200062, P. R. of China   Email: jzhou@chem.ecnu.edu.cn
,
Jian Zhou*
a   Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, 3663N Zhongshan Road, Shanghai 200062, P. R. of China   Email: jzhou@chem.ecnu.edu.cn
c   State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China
› Author AffiliationsFinancial support from the 973 program (2015CB856600) and ­National Natural Science Foundation of China (21472049) is appreciated.
Further Information

Publication History

Received: 12 March 2017

Accepted after revision: 22 May 2017

Publication Date:
12 July 2017 (online)

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◊ These authors contributed equally to this work

Abstract

Ph3PAuOTf was identified as a powerful catalyst for the ­Mukaiyama–Mannich reaction of fluorinated silyl enol ethers with α-amino sulfones. This provides ready access to β-amino α-fluorinated ketones in good to excellent yields.

Key words

Mukaiyama–Mannich reaction - fluorinated silyl enol ethers - amino sulfones - amino fluorinated ketones - gold catalysis

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1588475.
  • Supporting Information
 

  • References and Notes


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  • 15 Because Bi(OTf)3 was slightly inferior to Ph3PAuOTf in terms of the yield of 3a (Table 1), we also examined its performance in other solvents, such as ethyl acetate, toluene, or MeCN, but no better result was obtained (the yields of 3a were 21, 55, and 58%, respectively). When Bi(OTf)3 was used to mediate the reaction of the aliphatic aldehyde-derived sulfones 1k and 1l, the desired products 3k and 3l were obtained in 15 and 10% yield, respectively, which were much lower than those obtained by using the Au(I) catalyst.
  • 16 tert-Butyl (2,2-Difluoro-3-oxo-1,3-diphenylpropyl)carbamate (3a); Typical Procedure Under N2, a 25 mL dry Schleck tube was charged with Ph3PAuCl (0.0075 mmol, 3.7 mg) and AgOTf (0.0075 mmol, 1.9 mg), followed by anhyd DCE (2.5 mL). The solution was stirred at r.t. for about 15 min, and then the α-amino sulfone 1a (0.25 mmol) and the fluorinated silyl enol ether 2a (0.375 mmol) were added sequentially. The mixture was stirred at r.t. until 1a was fully converted (TLC), and then purified directly by flash column chromatography to give a white solid; yield: 80.4 mg (89%); mp 136–138 °C. 1H NMR (300 MHz, CDCl3): δ = 8.01–7.98 (m, 2 H), 7.65–7.60 (m, 1 H), 7.50–7.45 (m, 2 H), 7.36–7.34 (m, 5 H), 5.62–5.54 (m, 2 H), 1.40 (s, 9 H). 19F NMR (282 MHz, CDCl3): δ = –105.86 (d, J F–F = 275.8 Hz, 1 F), –107.06 (d, J F–F = 275.2 Hz, 1 F). 13C NMR (100 MHz, CDCl3): δ =188.88 (t, J C–F = 28.5 Hz), 154.70, 134.37, 133.90, 132.34 (t, J C–F = 1.9 Hz), 129.83 (t, J C–F = 3.5 Hz), 128.67, 128.56, 128.36, 116.78 (t, J C–F = 258.3 Hz), 80.47, 57.08 (t, J C–F = 24.5 Hz), 28.14.