Synlett 2013; 24(17): 2216-2220
DOI: 10.1055/s-0033-1339796
letter
© Georg Thieme Verlag Stuttgart · New York

New β-Hydroxy Acylsilane-Derived Building Blocks and Their Use in the Synthesis of Oxygen-Containing Heterocycles

Akondi Srirama Murthy
a   Université de Rennes 1, Institut des Sciences Chimiques de Rennes, CNRS UMR 6226, Avenue du Général Leclerc, 35042 Rennes Cedex, France
b   Natural Product Chemistry Division, CSIR-Indian Institute of Chemical Technology, Uppal Road, Tarnaka, Hyderabad, 500607, India   Fax: +33(2)23236978   Email: rene.gree@univ-rennes1.fr
,
Thierry Roisnel
a   Université de Rennes 1, Institut des Sciences Chimiques de Rennes, CNRS UMR 6226, Avenue du Général Leclerc, 35042 Rennes Cedex, France
,
Srivari Chandrasekhar
b   Natural Product Chemistry Division, CSIR-Indian Institute of Chemical Technology, Uppal Road, Tarnaka, Hyderabad, 500607, India   Fax: +33(2)23236978   Email: rene.gree@univ-rennes1.fr
,
René Grée*
a   Université de Rennes 1, Institut des Sciences Chimiques de Rennes, CNRS UMR 6226, Avenue du Général Leclerc, 35042 Rennes Cedex, France
› Author Affiliations
Further Information

Publication History

Received: 31 July 2013

Accepted after revision: 20 August 2013

Publication Date:
18 September 2013 (online)


Abstract

Starting from easily accessible β-hydroxy acylsilanes, several 1C-, 2C- and 3C-extension reactions have been developed to efficiently afford five new functionalized building blocks, which have been used for the preparation of several five- and six-membered lactones.

Supporting Information

 
  • References and Notes


    • For excellent reviews on the chemistry of acylsilanes, see:
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  • 11 CCDC 946755 contains the supplementary crystallographic data for compound 4. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
  • 12 Cuperly D, Petrignet J, Crévisy C, Grée R. Chem. Eur. J. 2006; 12: 3261
  • 13 de A Amaral P, Petrignet J, Gouault N, Agustini T, Lohézic-Ledévéhat F, Cariou A, Grée R, Eifler-Lima VL, David M. J. Braz. Chem. Soc. 2009; 20: 1687

    • For representative metal cyanide catalyzed reactions with acylsilanes, see:
    • 14a Linghu X, Johnson JS. Angew. Chem. Int. Ed. 2003; 42: 2534
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      For uses of La(CN)3 in acylsilane chemistry, see:
    • 15a Bausch CC, Johnson JS. J. Org. Chem. 2004; 69: 4283
    • 15b Linghu X, Bausch CC, Johnson JS. J. Am. Chem. Soc. 2005; 127: 1833
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  • 18 Preparation of Esters 3; General Procedure: To a mixture of β-hydroxy acylsilane (1 mmol), pyridine (2 mmol) and DMAP (0.2 mmol) in anhydrous CH2Cl2 (10 mL), acid chloride (1.2 mmol) was added slowly with stirring at room temperature. After stirring for 12 h, the reaction mixture was taken up in Et2O (50 mL) and washed with saturated CuSO4 (50 mL) solution. The organic layer was dried over anhydrous MgSO4 and concentrated. The liquid obtained was column purified to obtain pure compound. (1R*,2R*)-3-(tert-Butyldiphenylsilyl)-2-methyl-3-oxo-1-phenylpropyl Acetate (3a): Following the general experimental procedure, the reaction was performed with β-hydroxy acylsilane 1 (50 mg, 0.12 mmol), pyridine (20 μL, 0.24 mmol), DMAP (3 mg, 0.024 mmol) and AcCl (10 μL, 0.14 mmol) in anhydrous CH2Cl2 (1.2 mL) for 12 h at room temperature. The crude product was purified by silica gel column chromatography (EtOAc–pentane, 2%) to afford pure product 3a (45 mg, 81%) as a colorless oil. Rf = 0.8 (EtOAc–pentane, 10%). 1H NMR (300 MHz, CDCl3): δ = 7.61–7.58 (m, 2 H), 7.48–7.41 (m, 6 H), 7.36–7.34 (m, 2 H), 7.19–7.17 (m, 3 H), 6.91–6.88 (m, 2 H), 5.93 (d, J = 6.9 Hz, 1 H), 3.36 (quint, J = 6.9 Hz, 1 H), 1.98 (s, 3 H), 0.98 (s, 9 H), 0.84 (d, J = 6.9 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 245.2, 169.7, 139.4, 136.3, 131.8, 131.4, 130.0, 129.9, 128.1, 128.0, 127.6, 126.8, 74.1, 56.4, 27.6, 21.0, 18.7, 10.4. HRMS (ESI): m/z [M + Na]+ calcd for C28H32O3NaSi: 467.2018; found: 467.2016. (5S*,6R*)-5-Methyl-6-phenyl-5,6-dihydro-2H-pyran-2-one (10): To a stirred solution of 8 (15 mg, 0.03 mmol) in THF (0.4 mL) under a nitrogen atmosphere, was added TBAF (1 M in THF, 75 μL, 0.07 mmol) at 0 °C and the reaction was stirred at room temperature for 1 h. The reaction mixture was quenched by the addition of saturated aqueous NH4Cl (0.2 mL) solution, the organic layer was separated, and the aqueous layer was extracted with EtOAc (2 × 5 mL). The combined organic layer was washed with brine (5 mL), dried with Na2SO4, and the solvent was evaporated. The crude product was purified by silica gel column chromatography (EtOAc–pentane, 10%) to afford pure product 10 (6 mg, 85%) as a colorless oil. Rf = 0.2 (EtOAc–pentane, 10%). 1H NMR (300 MHz, CDCl3): δ = 7.42–7.30 (m, 5 H), 7.10 (dd, J = 6.2, 9.7 Hz, 1 H), 6.09 (d, J = 9.6 Hz, 1 H), 5.60 (d, J = 3.5 Hz, 1 H), 2.70–2.59 (m, 1 H), 0.82 (d, J = 7.1 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 164.5, 151.8, 137.0, 128.5, 128.0, 125.6, 120.0, 81.0, 34.8, 11.8. HRMS (ESI): m/z [M+Na]+ calcd for C12H12O2Na: 211.0735; found: 211.0732. (2R*,3R*)-1-(tert-Butyldiphenylsilyl)-3-(methoxy-methoxy)-2-methyl-3-phenylpropan-1-one (2): To a stirred, cooled (0 °C) solution of β-hydroxy acylsilane 1 (402 mg, 1.0 mmol) in CH2Cl2 (10 mL) were added N,N-diisopropylethylamine (0.5 mL, 3.0 mmol) and chloro-methyl methyl ether (114 μL, 1.5 mmol). The reaction mixture was allowed to reach room temperature over 12 h then treated with saturated aqueous NaHCO3 solution (5 mL) and the phases were separated. After extraction of the aqueous layer with CH2Cl2 (2 × 25 mL) the combined extracts were washed with brine (15 mL), dried (Na2SO4), and concentrated in vacuo. The crude product was purified by silica gel column chromatography (EtOAc–pentane, 2%) to afford pure product 2 (389 mg, 87%) as a colorless oil. Rf = 0.7 (EtOAc–pentane, 5%). 1H NMR (300 MHz, CDCl3): δ = 7.58–7.55 (m, 2 H), 7.49–7.36 (m, 4 H), 7.35–7.28 (m, 4 H), 7.22–7.17 (m, 3 H), 7.04–6.99 (m, 2 H), 4.72 (d, J = 8.2 Hz, 1 H), 4.37 (s, 2 H), 3.37 (quint, J = 7.0 Hz, 1 H), 3.22 (s, 3 H), 0.94 (d, J = 7.0 Hz, 3 H), 0.93 (s, 9 H). 13C NMR (75 MHz, CDCl3): δ = 246.7, 140.6, 136.4, 136.3, 132.1, 131.5, 130.0, 129.9, 129.7, 128.1, 128.0, 127.8, 127.5, 94.1, 57.6, 55.7, 27.6, 22.3, 18.6, 11.9. HRMS (ESI): m/z [M+Na]+ calcd for C28H34O3NaSi: 469.2175; found: 469.2172. (4R*,5R*,E)-Ethyl 3-(tert-Butyldiphenylsilyloxy)-5-(methoxymethoxy)-4-methyl-5-phenylpent-2-enoate (4): To a stirred solution of ethyl diazoacetate (15% in toluene, 160 μL, 0.22 mmol) and acylsilane 2 (100 mg, 0.22 mmol) in anhydrous THF (2 mL), was added LDA (2 M in heptane, 110 μL, 0.22 mmol) at –78 °C. After complete addition, the mixture was stirred for a further 30 min at the same temperature and then allowed to warm to 0 °C within 4 h. The reaction mixture was partitioned between EtOAc and saturated ammonium chloride, and the aqueous layer was extracted with EtOAc (3 × 10 mL). The combined organic layer was washed with brine (10 mL), dried with Na2SO4, and concentrated in vacuo. The crude product was purified by silica gel column chromatography (EtOAc–pentane, 6%) to afford pure product 4 (87 mg, 73%) as a white solid (mp 115 °C). Rf = 0.4 (EtOAc–pentane, 10%). 1H NMR (300 MHz, CDCl3): δ = 7.62–7.59 (m, 2 H), 7.44–7.29 (m, 9 H), 7.24–7.22 (m, 4 H), 4.76 (d, J = 9.6 Hz, 1 H), 4.67–4.57 (m, 1 H), 4.55–4.50 (m, 2 H), 4.42 (s, 1 H), 3.94–3.82 (m, 2 H), 3.37 (s, 3 H), 1.53 (d, J = 6.6 Hz, 3 H), 1.06 (s, 9 H), 1.04 (t, J = 7.1 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 171.0, 166.7, 139.5, 135.3, 130.9, 130.5, 130.1, 129.9, 128.7, 128.0, 127.9, 127.8, 127.7, 101.8, 93.9, 80.5, 59.1, 55.5, 41.2, 26.5, 19.5, 16.0, 14.2. HRMS (ESI): m/z [M+Na]+ calcd for C32H40O5NaSi: 555.2537; found: 555.2539. Mixture of (2S*,3R*,4R*)-2-(tert-Butyldiphenylsilyloxy)-4-(methoxymethoxy)-3-methyl-4-phenylbutanenitrile (5a) and (2R*,3R*,4R*)-2-(tert-Butyldiphenylsilyloxy)-4-(methoxymethoxy)-3-methyl-4-phenylbutanenitrile (5b): To a solution of 2 (200 mg, 0.44 mmol) in THF (4 mL) was added La(CN)3 (95 mg) by using a cannula at 0 °C and the mixture was stirred at the same temperature for 30 min. Upon completion of the reaction, saturated ammonium chloride solution (4 mL) was added and the mixture was extracted with EtOAc (3 × 20 mL). The combined organic layer was washed with brine (10 mL), dried with Na2SO4, and concentrated in vacuo. The crude product was purified by silica gel column chromatography (EtOAc–pentane, 3%) to afford 5 (160 mg, 80%) as an inseparable mixture of 65:35 syn/anti isomers 5a and 5b as a pale-yellow oil. Rf = 0.5 (EtOAc–pentane, 5%). 1H NMR (500 MHz, CDCl3): δ = 7.69–7.15 [m, 15 H (major), 15 H (minor)], 5.01 (d, J = 4.9 Hz, 1 H, major), 4.56 (dd, J = 6.7, 15.6 Hz, 2 H, major), 4.38 (dd, J = 6.7, 11.9 Hz, 2 H, minor), 4.31 (d, J = 8.7 Hz, 1 H, minor), 4.23 (d, J = 5.4 Hz, 1 H, major), 3.89 (d, J = 4.3 Hz, 1 H, minor), 3.37 (s, 3 H, major), 3.29 (s, 3 H, minor), 2.15–2.09 (m, 1 H, minor), 2.07–2.01 (m, 1 H, major), 1.41 (d, J = 6.5 Hz, 3 H, minor), 1.15 (s, 9 H, major), 1.06 (d, J = 7.9 Hz, 3 H, major), 1.15 (s, 9 H, minor). 13C NMR (100 MHz, CDCl3): δ = 139.6, 138.5, 136.0, 135.8, 135.6, 135.6, 131.9, 131.7, 131.5, 131.4, 131.4, 131.3, 130.4, 130.2, 130.2, 128.6, 128.3, 128.2, 128.1, 128.1, 128.0, 127.8, 127.6, 127.1, 127.0, 118.9, 117.9, 94.7, 94.0, 78.5, 76.0, 65.0, 64.9, 56.3, 55.8, 45.6, 45.4, 26.7, 19.4, 19.2, 11.2, 9.9. HRMS (ESI): m/z [M+Na]+ calcd for C29H35NO3NaSi: 496.2278; found: 496.2278. (3S*,4R*,5R*)-3-(tert-Butyldiphenylsilyloxy)-4-methyl-5-phenyldihydrofuran-2(3H)-one (15a) and (3R*,4R*,5R*)-3-(tert-Butyldiphenylsilyloxy)-4-methyl-5-phenyldihydrofuran-2(3H)-one (15b): A solution of 5 (150 mg, 0.32 mmol) in EtOH (10 mL) was cooled to 0 °C and acetyl chloride (3 mL) was added. The reaction was stirred for 1 h at the same temperature and the solvent was evaporated under vacuo. A dilute solution of sodium bicarbonate (10 mL) was added and the mixture was extracted with EtOAc (3 × 20 mL). The combined organic layer was washed with brine (10 mL), dried with Na2SO4, and concentrated in vacuo. The crude product was purified by silica gel column chromatography (EtOAc–pentane, 8%) to afford pure products 15a (62 mg, 46%) and 15b (33 mg, 24%) as colorless oils. Rf = 0.4 (EtOAc–pentane, 10%). Compound 15a: 1H NMR (300 MHz, CDCl3): δ = 7.78–7.75 (m, 2 H), 7.71–7.68 (m, 2 H), 7.48–7.38 (m, 6 H), 7.32–7.27 (m, 3 H), 7.09–7.06 (m, 2 H), 5.73 (d, J = 6.7 Hz, 1 H), 4.12 (d, J = 5.5 Hz, 1 H), 2.67–2.56 (m, 1 H), 1.14 (s, 9 H), 0.34 (d, J = 7.2 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 175.0, 136.0, 135.9, 135.7, 133.3, 132.1, 130.1, 128.4, 128.0, 127.7, 125.4, 81.9, 75.3, 43.3, 26.8, 19.3, 12.0. HRMS (ESI): m/z [M+Na]+ calcd for C27H30O3NaSi: 453.1862; found: 453.1863. Compound 15b: 1H NMR (300 MHz, CDCl3): δ = 7.85–7.82 (m, 2 H), 7.72–7.69 (m, 2 H), 7.50–7.28 (m, 9 H), 7.22–7.19 (m, 2 H), 5.27 (d, J = 4.7 Hz, 1 H), 4.67 (d, J = 6.8 Hz, 1 H), 2.58–2.47 (m, 1 H), 1.14 (s, 9 H), 0.69 (d, J = 7.2 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 174.9, 136.0, 135.7, 135.6, 133.2, 132.1, 130.1, 128.4, 127.9, 127.8, 125.2, 78.9, 73.5, 41.6, 26.7, 19.4, 8.1. HRMS (ESI): m/z [M+Na]+ calcd for C27H30O3NaSi: 453.1862; found: 453.1861.