Synlett 2014; 25(11): 1561-1564
DOI: 10.1055/s-0033-1339030
letter
© Georg Thieme Verlag Stuttgart · New York

Indium-Mediated Debromination of gem-Bromonitroalkanes under Mild Conditions in Aqueous Medium

Rita C. Acúrcio
Department of Chemistry & QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal   Fax: +351(234)370084   eMail: artur.silva@ua.pt   eMail: rsoengas@ua.pt
,
Raquel G. Soengas*
Department of Chemistry & QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal   Fax: +351(234)370084   eMail: artur.silva@ua.pt   eMail: rsoengas@ua.pt
,
Artur M. S. Silva*
Department of Chemistry & QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal   Fax: +351(234)370084   eMail: artur.silva@ua.pt   eMail: rsoengas@ua.pt
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Publikationsverlauf

Received: 15. März 2014

Accepted after revision: 08. April 2014

Publikationsdatum:
13. Mai 2014 (online)


Abstract

gem-Bromonitroalkanes are efficiently reduced into the corresponding dehalogenated products in excellent yields with indium metal in the presence of a palladium(0) catalyst and indium(III) chloride in aqueous medium. The addition of bromonitromethane to carbohydrate-derived aldehydes or imines, followed by debromination of the intermediate bromonitro compounds represents an extremely efficient method for the stereoselective preparation of nitrosugars.

Supporting Information

 
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  • 20 Nitroalkanes 2; General Procedure NaI (0.12 mmol, 0.15 equiv) was added to a stirred solution of bromonitromethane (0.8 mmol, 1 equiv) and the corresponding aldehyde 3 (0.8 mmol, 1 equiv) in THF (10 mL), and the resulting mixture was stirred at r.t. for 5 h. After this period, the mixture was quenched with aq HCl (10 mL, 0.1 M) and extracted with Et2O (1 × 20 mL). The combined extracts were washed with sat. aq Na2S2O3 solution (1 × 20 mL), dried over Na2SO4, filtered and the solvent removed under reduced pressure to afford the crude 1-bromo-1-nitroalkan-2-ol. In metal (183 mg, 1.6 mmol), InCl3 (88 mg, 0.4 mmol) and Pd(PPh3)4 (18 mg, 2 mol%) were added to a solution of the 1-bromo-1-nitroalkan-2-ol (0.8 mmol) in THF–H2O (2:1, 6 mL). After stirring the mixture at r.t. for 12 h, it was quenched with HCl (3 mL, 1 M), diluted with H2O (25 mL) and extracted with Et2O (3 × 25 mL). The combined organic extracts were dried over Na2SO4, filtered and the solvent removed under reduced pressure to afford the nitroalkanes 2.
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  • 23 N-(1-Cyclohexyl-2-nitroethyl)-4-methoxybenzenamine (2e) Brown oil; Rf  = 0.22 (hexane–EtOAc, 3:1). 1H NMR (300 MHz, CDCl3): δ = 6.76 (d, J = 9.0 Hz, 2 H), 6.65 (d, J = 9.0 Hz, 2 H), 4.72 (dd, J = 12.3, 5.2 Hz, 1 H), 4.46 (dd, J = 12.3, 7.4 Hz, 1 H), 4.08–4.04 (m, 1 H), 3.73 (s, 3 H), 2.73 (s, 11 H). 13C NMR (75 MHz, CDCl3): δ = 152.7 (C), 141.0 (C), 115.0 (2 × CH), 114.9 (2 × CH), 75.7 (CH2), 60.9 (CH), 55.7 (CH3), 43.0 (CH), 34.7 (2 × CH2), 25.2 (CH2), 21.6 (2 × CH2). MS (ESI): m/z (%) = 279 (6) [M + H]+, 234 (19), 216 (100), 214 (28). HRMS (ESI): m/z [M + H]+ calcd for C15H23N2O3: 279.1709; found: 279.1703.
  • 24 7-Deoxy-1,2:3,4-di-O-isopropylidene-7-nitro-d-glycero-β-d-galacto-heptopyranose (2g) Yellow oil; Rf  = 0.20 (hexane–EtOAc, 3:1); [α]D 20 –49.4 (c 0.6, CHCl3). 1H NMR (300 MHz, CDCl3): δ = 5.49 (d, J = 5.0 Hz, 1 H), 4.78 (apparent 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, CH 3), 1.46 (s, 3 H, CH 3), 1.37 (s, 3 H, CH 3), 1.32 (s, 3 H, CH 3). 13C NMR (75 MHz, CDCl3): δ = 109.6, 108.9, 96.2, 78.1, 70.6, 70.5, 70.1, 67.7, 67.4, 25.9, 24.8, 24.3. MS (ESI): m/z (%) = 342 (24) [M + Na]+, 337 (100) [M + NH4]+, 320 (19) [M + H]+, 262 (48).