Synlett 2017; 28(14): 1748-1752
DOI: 10.1055/s-0036-1590977
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© Georg Thieme Verlag Stuttgart · New York

Sharpless Asymmetric Dihydroxylation on α,β-Unsaturated Diazoketones: A New Entry for the Synthesis of Disubstituted Furanones

Alexánder G. Talero
Instituto de Química de São Carlos, Universidade de São Paulo, CEP 13560-970, São Carlos, SP, Brazil   Email: antonio@iqsc.usp.br
,
Instituto de Química de São Carlos, Universidade de São Paulo, CEP 13560-970, São Carlos, SP, Brazil   Email: antonio@iqsc.usp.br
› Author Affiliations
We would thank FAPESP (Research Supporting Foundation of the State of Sao Paulo) for financial support (2013/25504-1; 2013/18009-4)
Further Information

Publication History

Received: 31 May 2017

Accepted after revision: 10 July 2017

Publication Date:
15 August 2017 (online)


Published as part of the ISHC Conference Special Section

Abstract

The synthesis of enantiomerically pure 4,5-disubstituted 2-furanones is accomplished in three steps from aldehydes. The steps involve a highly enantioselective Sharpless asymmetric dihydroxylation of α,β-unsaturated diazoketones, followed by a photochemical Wolff rearrangement.

Supporting Information

 
  • References and Notes

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  • 19 General Procedure for the Synthesis of 4,5-Disubstituted 2-Furanones: In a quartz cell of 1 cm light path, containing a magnetic stirrer and fitted with a rubber septum, was added the diol (0.1 mmol) and anhydrous acetonitrile (2.5 mL, 0.04 M) under argon atmosphere. The reaction mixture was irradiated with an Osram 150 xenon arc lamp for 10 h under magnetic stirring at room temperature. The solvent was then removed under reduced pressure in a rotatory evaporator and the crude product was purified by flash chromatography with a short pad of silica (CHCl3 as the eluent). Lactones were obtained as solids. (4S,5S)-4-Hydroxy-5-phenyldihydrofuran-2(3H)-one [(+)-10]: Yield: 16 mg (90% yield); pale-yellow solid; mp 78–80 °C; Rf = 0.2 (silica gel, CHCl3, twice eluted); IR: 3432, 2929, 1773, 1454, 1310, 1154, 1075, 1020, 742, 699 cm–1; 1H NMR (500 MHz, CDCl3): δ = 7.47–7.43 (m, 2 H), 7.42–7.37 (m, 3 H), 5.52 (d, J = 3.5 Hz, 1 H), 4.63 (m, 1 H), 2.90 (dd, J = 17.5, 5.1 Hz, 1 H), 2.74 (d, J = 17.5 Hz, 1 H), 1.48 (s, 1 H); 13C NMR (101 MHz, CDCl3): δ = 175.3, 132.3, 129.1, 129.0, 126.3, 85.0, 70.2, 38.5; [α] d 25 +34.4 (c = 0.98, MeOH); HPLC conditions: Lux® amilose-2 8:2 (n-hexane/IPA); flow rate: 1.1 mL/min; λ = 206 nm; t R = 18.58 (major), 22.06 (minor) min; e.r. = 98:02.
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