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

  • 1 Burtoloso AC. B. Dias RM. P. Bernardim B. Acc. Chem. Res. 2015; 48: 921
  • 2 Pinho VD. Burtoloso AC. B. J. Org. Chem. 2011; 76: 289
  • 3 Rosset IG. Burtoloso AC. B. J. Org. Chem. 2013; 78: 9464
  • 4 Rulev AY. Russ. Chem. Rev. 2011; 80: 197
  • 7 Vanrheenen V. Kelly RC. Cha DY. Tetrahedron Lett. 1976; 23: 1973
    • 8a Smith DA. Reynolds DN. Woo LK. J. Am. Chem. Soc. 1993; 115: 2511
    • 8b Demonceau A. Lemoine CA. Noels AF. Tetrahedron Lett. 1996; 37: 1025
    • 9a Sharpless KB. Amberg W. Benani YL. Crispino GA. Hartung J. Jeong K-S. Kwong H.-L. Morikawa K. Wang Z.-M. Xu D. Zhang X.-L. J. Org. Chem. 1992; 57: 2768
    • 9b Kolb H. VanNieuwenhze MS. Sharpless KB. Chem. Rev. 1994; 94: 2483
  • 10 Minato M. Yamamoto K. Tsuji J. J. Org. Chem. 1990; 55: 766
  • 11 Eames J. Mitchell HJ. Nelson A. O’brien P. Warren S. Wyatt P. J. Chem. Soc., Perkin Trans. 1 1999; 1095
  • 12 Junttila MH. Hormi OO. E. J. Org. Chem. 2009; 74: 3038
  • 13 Jacobsen EN. Markó I. Mungall WS. Schröder G. Sharpless KB. J. Am. Chem. Soc. 1988; 110: 1968
  • 14 General Procedure for Asymmetric Dihydroxylation of α,β-Unsaturated Diazoketones: To a 3 mL glass vial containing a magnetic stirrer and fitted with a cap, was added 418 mg of an oxidizing mixture containing K3Fe(CN)6 (6 equiv, 286.8 mg, 0.87 mmol), K2CO3 (6 equiv, 120.4 mg, 0.87 mmol), (DHQ)2PHAL (11.3 mg, 0.0145 mmol), and K2OsO2(OH)4 (0.214 mg, 0.0581 mmol). Then, a t-BuOH/H2O mixture (1:2, 1.5 mL) was added and the mixture was vigorously stirred. CH3SO2NH2 (3 equiv, 41.4 mg, 0.435 mmol) and α,β-unsaturated diazoketone (1 equiv, 0.145 mmol) were added and the mixture was allowed to react for 10 hours. After this time, another portion of the oxidizing mixture (418 mg) and CH3SO2NH2 (41.4 mg) were added and the mixture was stirred for an additional 10 h (progress of the reaction monitored by TLC). After this time, H2O (30 mL) was added to the reaction mixture and the aqueous phase was extracted with a mixture of CH2Cl2 and 2-propanol (3:1, 2 × 10 mL), followed by another extraction with pure CH2Cl2 (3 × 10 mL) (conventional work-up with Na2SO3 and base led to degradation of the products). The organic phase was dried over Na2SO4, filtered and concentrated. The products were purified by flash chromatography (silica gel, 1:1 hexane/EtOAc) to afford the pure solid diols (Note: all racemic diols were synthesized by using DABCO as the ligand in similar yields; For larger scales, the conditions described in Table 1, entry 14, was preferred). (3R,4S)-1-Diazo-3,4-dihydroxy-4-phenylbutan-2-one [(+)-2]: Yield: 16 mg (53% yield; 57% based on recovery of starting material; diazoketone recovered: 1.5 mg); crystalline yellow solid; mp 97–99 °C; Rf = 0.15 (silica gel, 1:1 EtOAc/hexane); IR: 3332, 3268, 3118, 2918, 2115, 1599, 1363, 1300, 1140, 1047, 708 cm–1; 1H NMR (500 MHz, CD3CN): δ = 7.40–7.32 (m, 4 H), 7.27 (tt, J = 7.2, 1.3, 1.3 Hz, 1 H), 5.88 (s, 1 H), 4.95 (dd, J = 5.5, 2.9 Hz, 1 H), 4.16 (d, J = 3.3 Hz, 1 H), 3.74 (d, J = 6.8 Hz, 1 H), 3.64 (d, J = 5.9 Hz, 1 H); 13C NMR (126 MHz, CD3CN): δ = 196.6, 142.4, 128.9, 128.3, 127.4, 80.2, 74.8, 54.5; [α] d 25 +141.6 (c = 0.5, MeOH); HRMS (ESI-TOF): m/z [M++Na] calcd for C10H10N2NaO3: 229.05836; found: 229.05801; HPLC conditions: Chiralpak AD-H, 1:1 (n-hexane/IPA); flow rate: 1.0 mL/min; λ = 254 nm; t R = 4.60 (minor), 8.74 (major) min; e.r. = 99:1.
  • 15 Carter NB. Nadany AE. Sweeney JB. J. Chem. Soc., Perkin Trans. 1 2002; 2324
    • 16a Shah NC. Pringle SD. Donan PT. Struthers AD. J. Hypertens. 2007; 25: 2345
    • 16b Raju R. Gromyko O. Fedorenko V. Herrmann J. Luzhetskyy A. Müller R. Tetrahedron Lett. 2013; 54: 900
    • 16c Yabu Y. Yoshida A. Suzuki T. Nihei C. Kawai K. Minagawa N. Hosokawa T. Nagai K. Ohta N. Parasitol. Int. 2003; 52: 155
  • 17 Ledroit V. Debitus C. Lavaud C. Massiot G. Tetrahedron Lett. 2003; 44: 225
    • 18a Kuroda I. Musman M. Ohtani II. Ichiba T. Tanaka J. Gravalos DC. Higa T. J. Nat. Prod. 2002; 65: 1505
    • 18b Martinková M. Gonda J. Carbohydr. Res. 2016; 423: 1
  • 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.
    • 20a Wang Z.-M. Zhang X.-L. Sharpless KB. Sinha SC. Sinha-Bagchi A. Keinan E. Tetrahedron Lett. 1992; 33: 6407
    • 20b Reddy GV. Sreevani V. Iyengar DS. Tetrahedron Lett. 2001; 42: 531
    • 20c Eissler S. Nahrwold M. Neumann B. Stammler H.-G. Sewald N. Org. Lett. 2007; 9: 817