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Synlett 2012; 23(14): 2083-2086
DOI: 10.1055/s-0031-1290441
DOI: 10.1055/s-0031-1290441
letter
Synthesis of Sugar-Derived 2-Nitroalkanols via Henry Reaction Promoted by Samarium Diiodide or Indium
Weitere Informationen
Publikationsverlauf
Received: 15. Mai 2012
Accepted after revision: 18. Juni 2012
Publikationsdatum:
08. August 2012 (online)
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Abstract
We present herein an improved synthesis of nitro sugars, consisting of a Henry-type reaction of bromonitromethane and sugar aldehydes. The reaction can be promoted by either SmI2 or indium metal, yielding in both cases high yields and good diastereoisomeric ratios. However, while the SmI2-promoted reaction is very sensitive to steric factors and only gives satisfactory results with bromonitromethane, the indium-mediated reaction is not subjected to this limitation, giving excellent results with bromonitromethane as well as more hindered bromonitroalkanes.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
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References
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- 17 Representative Analytical Data 3-O-Benzyl-6-deoxy-6-nitro-1,2-O-isopropyliden-α-d-glucofuranose (3a) Yellow oil; [α]D 20 –26.8 (c 1.0 in CHCl3). 1H NMR (300 MHz, CDCl3): δ = 7.49–7.30 (m, 5 H), 5.91 (d, J = 3.7 Hz, 1 H), 4.76–4.60 (m, 4 H), 4.56–4.42 (m, 2 H), 4.14–4.06 (m, 2 H), 2.58 (d, J = 4.9 Hz, 1 H), 1.47 (s, 3 H), 1.32 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 136.8 (C), 128.8 (2 × CH), 128.4 (CH), 127.9 (2 × CH), 112.1 (C), 105.1 (CH), 82.0 (CH), 80.9 (CH), 79.9 (CH), 78.5 (CH2), 72.1 (CH2), 66.3 (CH), 26.9 (CH3), 26.1 (CH3) ppm. MS (ESI+): m/z (%) = 362 (15) [M + Na]+, 357 (100) [M + NH4]+, 316 (1), 288 (8), 282 (1). HRMS (ESI+): m/z calcd for [C16H21NO7Na]+ [M + Na]+: 362.1216; found: 362.1210; Rf = 0.33 (hexane–EtOAc = 3:1). 7-Deoxy-1,2:3,4-di-O-isopropylidene-7-nitro-d -glycero-β-d-galacto-heptopyranose (3c) Yellow oil; [α]D 20 –49.4 (c 0.6 in CHCl3). 1H NMR (300 MHz, CDCl3): δ = 5.49 (d, J =5.0 Hz, 1 H), 4.78 (app d, J = 11.2 Hz, 1 H), 4.65 (dd, J = 8.0, 2.5 Hz, 1 H), 4.51–4.47 (m, 2 H), 4.43 (dd, J = 8.0, 2.0 Hz, 1 H), 4.34 (dd, J = 4.9, 2.5 Hz, 1 H), 3.73 (dd, J = 8.2, 2.0 Hz, 1 H), 2.89 (d, J = 5.9 Hz, 1 H), 1.51 (s, 3 H), 1.46 (s, 3 H), 1.37 (s, 3 H), 1.32 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 109.6 (C), 108.9 (C), 96.2 (CH), 78.1 (CH2), 70.6 (CH), 70.5 (CH), 70.1 (CH), 67.7 (CH), 67.4 (CH), 25.9 (2 × CH3), 24.8 (CH3), 24.3 (CH3) ppm. MS (ESI+): m/z (%) = 342 (24) [M + Na]+, 337 (100) [M + NH4]+, 320 (19) [M + H]+, 262 (48). HRMS (ESI+): m/z calcd for [C13H22NO8]+ [M + H]+: 320.1340; found: 320.1339. Rf = 0.20 (hexane–EtOAc = 3:1).
- 18 General Procedure for the Samarium Diiodide Mediated Reaction of Bromonitromethane and Aldehydes SmI2 (0.8 mmol, 0.1 M) in THF (8 mL) was added to a stirred solution of bromonitromethane (0.8 mmol) and the corresponding aldehyde (0.8 mmol) in THF (5 mL). After stirring the reaction mixture at r.t. for 5 h it was quenched with aq HCl (10 mL, 0.1 M) and extracted with CH2Cl2 (3 × 25 mL). The combined extracts were washed with an aq sat. solution of Na2S2O3 (20 mL), then dried over MgSO4, filtered, and the solvent was evaporated in vacuo. The residue was purified by flash column chromatography with mixtures of EtOAc–hexane.
- 19 General Procedure for the Indium-Mediated Reaction of Bromonitroalkanes and Aldehydes To a suspension of indium powder (0.5 mmol) in THF (1 mL) was added the bromonitroalkane (0.6 mmol), and the mixture was sonicated for 20 min. The corresponding aldehyde (0.5 mmol) was added, and sonication was continued for a further 4 h. The reaction mixture was neutralized with sat. aq NaHCO3, diluted with H2O (10 mL), and extracted with Et2O (3 × 25 mL). The combined organic layers were dried over MgSO4, filtered, and the solvent was evaporated in vacuo. The residue was purified by flash column chromatography with mixtures of EtOAc–hexane.
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21
Representative Analytical Data
1-O-tert-Butyldimethylsilyl-2,3-di-O-isopropylidene-5(R)-(1-methyl-1-nitroethyl)-α-d-lyxofuranose (5c) Yellow oil; [α]D 23 –21.3 (c 0.4 in CHCl3). 1H NMR (300 MHz, CDCl3): δ = 5.09 (s, 1 H, 1-H), 4.84 (dd, 1 H, J = 3.8, 5.8 Hz), 4.53–4.63 (m, 2 H), 3.80–4.48 (m, 2 H), 2.85 (d, 1 H, J = 5.6 Hz, OH), 1.61 (s, 6 H, 2 × CH3), 1.31, 1.47 (2 × s, 6 H, 2 × CH3), 0.86 (s, 9 H, 3 × CH3), 0.10 (s, 3 H, CH3), 0.11 (s, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 113.12 (C), 106.13 (CH), 91.1 (C), 84.3 (CH), 81.1 (CH), 79.3 (CH), 73.9 (CH), 69.6 (CH), 26.3 (CH3), 25.0 (CH3), 24.0 (CH3), 21.0 (CH3), 19.8 (C), 17.8 (3 × CH3), –4.5 (CH3), –5.5 (CH3) ppm. ESI-MS: m/z (%) = 488 (10) [M + H]+. HRMS: m/z calcd for C26H38NO6Si [M + H]+: 488.2462; found: 488.2471. Rf = 0.30 (hexane–EtOAc = 7:1). 4-O-tert-Butyldiphenylsilyl-2,3-di-O-isopropylidene-1(S)-(1-methyl-1-nitroethyl)-d-threitol (5e) Yellow oil. 1H NMR (300 MHz, CDCl3): δ = 7.66–7.73 (m, 4 H, 4 × HAr), 7.35–7.48 (m, 6 H, 6 × HAr), 4.10–4.23 (m, 2 H), 3.83–3.90 (m, 2 H), 3.66–3.74 (m, 1 H), 1.67, 1.69 (2 × s, 6 H, 2 × CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 135.7 (C), 135.6 (C), 128.1 (CH), 128.0 (CH), 127.8 (CH), 127.7 (CH), 127.6 (CH), 110.2 (C), 91.3 (C), 81.0 (CH), 79.6 (CH), 76.3 (CH), 65.2 (CH2), 26.7 (CH3), 26.6 (CH3), 23.3 (CH3), 21.6 (CH3), 19.3 (CH3) ppm. ESI-MS: m/z (%) = 505 (100) [M + Na]+: 488 (20) [M + H]+. HRMS: m/z calcd for C26H38NO6Si [M + H]+: 488.2462; found: 488.2484. Rf = 0.29 (hexane–EtOAc = 4:1). -
22
Representative Analytical Data
3-O-Benzyl-5(R)-(2,2-dimethyl-5-nitro-1,3-dioxan-5-yl)-1,2-O-isopropylidene-α-d-xylofuranose (7a) Yellow oil; [α]D 24 –39.7 (c 1.2 in CHCl3). 1H NMR (300 MHz, CDCl3): δ = 7.36–7.24 (m, 5 H, 5 × HAr), 5.91 (d, 1 H, J 1,2 = 3.7 Hz, 1-H), 4.42–4.57 (m, 5 H), 4.05–4.34 (m, 5 H), 1.34, 1.39, 1.43, 1.45 (4 × s, 12 H, 4 × CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 136.8 (C), 129.2 (2 × CH), 128.9 (CH), 128.3 (2 × CH), 112.6 (C), 105.6 (C), 99.5 (CH), 90.2 (C), 82.5 (CH), 81.3 (CH), 78.7 (CH2), 72.4 (CH), 70.4 (CH), 62.8 (CH2), 61.1 (CH2), 26.5 (CH3), 25.6 (CH3), 21.5 (CH3), 20.6 (CH3) ppm. ESI-MS: m/z (%) = 440 (21) [M + H]+, 462 (100) [M + Na]+. HRMS: m/z calcd for C21H30NO9 [M + H]+: 440.1915; found: 440.1894. Rf = 0.31 (hexane–EtOAc = 3:1). 1,2:3,4-Di-O-isopropylidene-6(R)-(2,2-dimethyl-5-nitro-1,3-dioxan-5-yl)-β-d-galacto-heptopyranose (7b) Colorless oil; [α]D 25 +33.4 (c 0.9 in CHCl3). 1H NMR (300 MHz, CDCl3): δ = 5.50 (d, 1 H, J = 5.1 Hz, H-1), 4.52–4.71 (m, 3 H), 4.03–4.37 (m, 5 H), 3.92 (dd, 1 H, J = 8.9, 1.9 Hz,), 3.16 (d, 1 H, J = 7.1 Hz, OH), 1.33, 1.35, 1.36, 1.45, 1.46, 1.59 (6 × s, 18 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 109.6 (C), 109.1 (C), 98.9 (C), 96.1 (CH), 89.9 (C), 70.8 (CH), 70.6 (CH), 70.5 (CH), 70.0 (CH), 66.6 (CH), 62.7 (CH2), 61.1 (CH2), 27.3 (CH3), 25.8 (CH3), 25.6 (CH3), 24.3 (CH3), 19.5 (CH3) ppm. ESI-MS: m/z (%) = 420 (31) [M + H]+, 442 (9) [M + Na]+. HRMS: m/z calcd for C18H30NO10 [M + H]+: 420.1870; found: 420.1863. Rf = 0.31 (hexane–EtOAc = 2:1).
Reactions of bromonitromethane and aldehydes to give 2-bromo-2-nitroalkan-1-ols have also been described:
Reviews on indium chemistry: