J. Gratien et al. / Carbohydrate Research 343 (2008) 18–30
29
77.6 (C-2), 76.3 (C-3), 74.1 (CH2Ph), 73.9 (2C, CH2Ph),
73.7 (CH2Ph), 68.4 (C-6).
allow us to propose MgIOEt as the reactive Mg species
involved in the epimerization reaction.
3.21.1.2. MgI2-complexed gluconolactone. IR (neat,
cmꢁ1) 3396, 1644, 1453, 1094; 1H NMR (CDCl3) d
7.47–7.13 (m, 20H), 5.34 (br s, 1H), 5.28 (br s, 1H),
4.84 (br s, 1H), 4.76 (br s, 1H), 4.55–4.07 (m, 6H),
3.61–3.59 (m, 1H), 3.50–3.40 (m, 1H); 13C NMR
(CDCl3) d 179.8, 136.3–136.5, 129.3–127.8, 84.0, 80.1,
77.2, 75.2, 74.4, 73.4, 72.7, 67.7, 53.4; ESITOF-MS
(M+EtOMgI+H)+, m/z 735.
Supplementary data
1H and 13C NMR spectra of 1, 7, 10, 11, 13, 15, 17, 19,
20, and NMR spectra of the magnesium–aldonolactone
complexes. Supplementary data associated with this
article can be found, in the online version, at
3.21.2. Analysis of the MgI2-complexed mannonolactone
compared to 2,3,4,6-tetra-O-benzyl-D-mannono-1,5-
lactone (7)
References
3.21.2.1. 2,3,4,6-Tetra-O-benzyl-D-mannono-1,5-lac-
tone (7). IR (neat, cmꢁ1) 2868, 1755, 1453, 1094, 698;
1H NMR (CDCl3) d 7.39–7.09 (m, 20H, Ph), 5.07 (d,
J = 11.9 Hz, 1H, CH2Ph), 4.84 (d, J = 11.2 Hz, 1H,
CH2Ph), 4.65 (d, J = 11.2 Hz, 1H, CH2Ph), 4.59 (d,
J = 11.9 Hz, 1H, CH2Ph), 4.54 (s, 2H, CH2Ph), 4.29
(d, J = 2.7 Hz, 1H, H-2), 4.30–4.16 (m, 2H, CH2Ph),
4.20–4.16 (m, 1H, H-5), 3.99 (dd, J = 1.7, 2.6 Hz, 1H,
H-3), 3.73 (dd, J = 1.6, 7.2 Hz, 1H, H-4), 3.58 (d,
J = 4.6 Hz, 2H, H-6); 13C NMR (CDCl3) d 169.3 (C-
1), 137.7 (2C, Ph), 137.2 (Ph), 136.8 (Ph), 128.4–127.7
(Ph), 78.6 (C-5), 77.0 (C-3), 76.1 (C-4), 75.7 (C-2), 73.7
(CH2Ph), 72.9 (2C, CH2Ph), 71.3 (CH2Ph), 69.2 (C-6).
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MgI2-complexed
mannonolactone. IR
(neat, cmꢁ1) 3416, 1630, 1453, 1092, 619; 1H NMR
(CDCl3) d 7.68–7.54 (m, 2H), 7.44–6.95 (m, 18H),
5.51–5.38 (m, 1H), 5.21–5.09 (m, 1H), 4.93 (br s, 1H),
4.56–4.36 (m, unclear), 3.85–3.75 (m, 1H), 3.64 (d,
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Freshly prepared magnesium species in the epimeriza-
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)