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Synlett 2017; 28(15): 2018-2023
DOI: 10.1055/s-0036-1588833
letter
© Georg Thieme Verlag Stuttgart · New York

I2/TBHP-Promoted Approach to α-Keto Esters from Trifluoromethyl β-Diketones and Alcohols via C–C Bond Cleavage

Tongle Shao
a   Laboratory for Advanced Material and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China   Email: fangxiang@ecust.edu.cn   Email: yxy@ecust.edu.cn
,
Xiang Fang*
a   Laboratory for Advanced Material and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China   Email: fangxiang@ecust.edu.cn   Email: yxy@ecust.edu.cn
,
Jun Zhou
a   Laboratory for Advanced Material and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China   Email: fangxiang@ecust.edu.cn   Email: yxy@ecust.edu.cn
,
Chen Jin
a   Laboratory for Advanced Material and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China   Email: fangxiang@ecust.edu.cn   Email: yxy@ecust.edu.cn
,
Xueyan Yang*
a   Laboratory for Advanced Material and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China   Email: fangxiang@ecust.edu.cn   Email: yxy@ecust.edu.cn
,
Fanhong Wu
b   School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 120 Caobao Road, Shanghai 200235, P. R. of China
› Author AffiliationsThe authors thank the National Natural Science Foundation of China (No. 21672151) for financial support.
Further Information

Publication History

Received: 01 March 2017

Accepted after revision: 24 April 2017

Publication Date:
16 May 2017 (online)

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Abstract

A metal-free oxidative coupling reaction of trifluoromethyl β-diketones with alcohols for the synthesis of α-keto esters in good to excellent yields has been developed. Preliminary mechanistic studies suggest that an I2/TBHP promoted sequential iodination, C–C bond cleavage, C–O bond formation and oxidation pathway is involved in this reaction.

Key words

trifluoromethyl β-diketones - α-keto esters - C–C bond cleavage - C–O coupling - alcohols

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1588833.
  • Supporting Information
 

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  • 17 Typical Procedure for the Synthesis of 3 from 1 To a mixture of 1k (126 mg, 0.5 mmol), methanol 2a (48 mg, 1.5 mmol), I2 (140 mg, 0.55 mmol), tert-butyl hydroperoxide (112.7 mg, 1.25 mmol) and Na2CO3 (53 mg, 0.5 mmol) was added 1,2-dichloroethane (1.5 mL) at room temperature. The reaction mixture was then stirred at 60 °C for 7 h. When the reaction was complete (monitored by TLC), the reaction was quenched with 2 mL of saturated NH4Cl and 4 mL of saturated Na2S2O3 aqueous solution. After extraction with EtOAc and drying with Na2SO4, the organic layer was concentrated under reduced pressure and the residue was purified by column chromatography on silica gel using hexanes/EtOAc (100:1 to 50:1) as eluent to afford the desired products 3ak (99 mg, 99% yield). Methyl 2-(3,4-Difluorophenyl)-2-oxoacetate (3ak) White solid; m.p. 38.7–40.2 °C. 1H NMR (400 MHz, CDCl3): δ = 7.96–7.91 (m, 1 H), 7.90–7.86 (m, 1 H), 7.34–7.28 (m, 1 H), 3.99 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 182.9, 162.9, 154.8 (dd, J 1 = 261.6 Hz, J 2 = 13.1 Hz), 150.5 (dd, J 1 = 253.5 Hz, J 2 = 13.1 Hz), 129.5 (t, J = 4.0 Hz), 127.7 (dd, J 1 = 8.1 Hz, J 2 = 4.0 Hz), 119.3 (dd, J 1 = 18.2 Hz, J 2 = 2.0 Hz), 117.9 (d, J = 18.2 Hz). 19F NMR (CDCl3, 376 MHz): δ = –125.53 to –125.65 (m, 1 F), –134.76 to –134.87 (m, 1 F). EI-MS: m/z (%) = 63, 93, 113, 141 (100), 142, 153, 172, 184, 200. HRMS: m/z calcd for [C9H6F2O3]+: 200.0285; found: 200.028.