Preparation of a methyl 3,4-dideoxy-3-C-nitro-α-d-threo-hex-3-enopyranoside bearing a peroxy function at C-2 and its reactions with some nucleophiles

Synthesis of Deoxyglycosides by Desulfurization under UV Light

“…Methyl 2,4-Dideoxy-β-D-threo-hexopyranoside 24. In a solution of methyl 2,4-dithio-β-D-mannopyranoside 23 36 (102 mg, 0.46 mmol) and P(Et) 3 (252 μL, 1.48 mmol) in DMF(1 mL), performed as described in the general procedure of desulfurization reaction under UV light, 24 was obtained as colorless oil (elution with methanol/ethyl acetate = 1:50 (v/v); 41 mg, 55% yield): [α] D 25 = +22.5 (c = 2.0 in CH 3 OH); 1 H NMR (400 MHz, D 2 O) δ = 4.40 (dd, J = 2.0, 9.2 Hz, 1H, H-1), 3.84 (m, 1H, H-3), 3.61−3.44 (m, 3H, H-5, H-6a, H-6b), 3.40 (s, 3H, OMe), 2.08 (ddd, J = 12.0 Hz, 1H, H-2a), 1.78 (d, J = 12.4 Hz, 1H, H-4a), 1.19−0.96 (m, 2H, H-2b, H-4b) ppm; 13 C NMR (100 MHz, CD 3 OD) δ = 101.3, 72.9, 65.9, 64.5, 55.3, 40.4, 36.2 ppm; IR (film) ν = 3388, 2923, 1645, 1460, 1383, 1175, 1029, 669 cm −1 ; HRMS (ESI-TOF) m/z [M + Na] + calcd for C 7 H 14 O 4 Na 185.0790; found 185.0786.Methyl 2,4-Dideoxy-α-D-threo-hexopyranoside 26 64. In a solution of methyl 2,4-dithio-α-D-mannopyranoside 2536 (110 mg, 0.49 mmol) and P(Et) 3 (265 μL, 1.56 mmol) in DMF (1 mL), performed as described in the general procedure of desulfurization reaction under UV light, 26 was obtained as colorless oil (elution with methanol/ethyl acetate = 1:50 (v/v); 46 mg, 58% yield):[α] D 25 = +166.8 (c = 1.2 in CH 3 OH); 1 H NMR (400 MHz, D 2 O) δ = 4.89 (d, J = 3.6 Hz, 1H, H-1), 3.98 (m, 1H, H-3), 3.77 (m, 1H, H-5), 3.58 (dd, J = 3.2 Hz, 12.0 Hz, 1H, H-6a), 3.50 (dd, J = 6.4 Hz, 12.0 Hz, 1H, H-6b), 3.25 (s, 3H, OMe), 1.98 (m, 1H, H-2a), 1.84 (m, 1H, H-4a), 1.45 (ddd, J = 3.6 Hz, 11.6 Hz, 15.2 Hz, 1H, H-2b), 1.21 (q, J = 11.6 Hz, 1H, H-4b) ppm; 13 C NMR (100 MHz, D 2 O) δ = 99.0, 68.9, 64.2, 62.9, 54.3, 37.5, 35.2 ppm; IR (film) ν = 3393, 2923, 1630, 1451, 1383, 1166, 1083, 669 cm −1 ; HRMS (ESI-TOF) m/z [M + Na] + calcd for C 7 H 14 O 4 Na 185.0790; found 185.0789. h i b i t e d .…”