R. Riguera et al.
11.9 Hz, 1H), 4.46 (s, 1H), 4.8 (s, 1H), 6.06 (dd, J=3.8, 8.2 Hz, 1H),
7.20–7.50 ppm (m, 15H); 13C NMR (62.83 MHz, CDCl3): d=57.8, 57.8,
66.6, 74.2, 82.5, 82.9, 127.0, 127.6, 127.6, 127.8, 128.9, 129.1, 129.1, 129.2,
129.2, 135.9, 136.4, 136.6, 170.2, 170.6 ppm; MS (EI): m/z: 434 [M+].
1H), 7.29–7.38 ppm (m, 15H); 13C NMR (62.83 MHz, CDCl3): d=27.5,
27.6, 57.5, 62.7, 73.0, 76.6, 77.7, 78.2, 82.3, 82.5, 104.4, 113.9, 127.5, 127.8,
128.7, 128.9, 129.1, 129.5, 136.0, 136.9, 151.8, 169.5, 170.2 ppm; MS (EI):
m/z: 620 [M+].
Bis-(S)-MPA ester of (R)-1-phenylethane-1,2-diol ((S)-9): [a]D =+42.67
(c=1.21 in CHCl3); 1H NMR (250.17 MHz CDCl3) d=3.36 (s, 3H), 3.37
(s, 3H), 4.31 (dd, J=4.1 Hz, 11.9 Hz, 1H), 4.36 (dd, J=6.6 Hz, 11.9 Hz,
1H), 4.68 (s, 2H), 5.95 (dd, J=4.6, 6.5 Hz, 1H), 6.89–7.36 ppm (m, 15H);
13C NMR (62.83 MHz, CDCl3): d=57.6, 57.7, 66.6, 74.1, 82.7, 126.6,
127.6, 127.8, 128.8, 128.8, 129.1, 129.2, 129.3, 129.8, 136.3, 136.4, 169.8,
170.6 ppm; MS (EI): m/z: 434 [M+].
Bis-(S)-MPA ester of (Z)-3-benzyloxyimine-3-deoxy-1,2-O-isopropyli-
den-a-d-glucofuranose ((S)-13): [a]D =+245.30 (c=0.075 in CHCl3);
1H NMR (250.17 MHz, CDCl3): d=1.32 (s, 3H), 1.37 (s, 3H), 3.29 (s,
3H), 3.31 (s, 3H), 3.83 (dd, J=8.2 Hz, 11.7 Hz, 1H), 4.21 (dd, J=5.7 Hz,
11.7 Hz, 1H), 4.44 (s, 1H), 4.73 (s, 1H), 4.85 (d, 3.5 Hz, 1H), 5.15 (brs,
2H), 5.15–5.19 (m, 1H), 5.54 (d, J=4.7 Hz, 1H), 5.60–5.65 (m, 1H),
7.28–7.42 ppm (m, 15H); 13C NMR (62.83 MHz, CDCl3): d=27.4, 57.4,
62.7, 71.6, 76.3, 78.1, 82.0, 82.2, 104.5, 113.9, 126.9, 127.1, 128.2, 128.4,
128.5, 128.6, 128.7, 128.8, 135.7, 136.6, 156.6, 157.6, 169.6 ppm; MS (EI):
m/z: 620 [M+].
Bis-(R)-MPA ester of (R)-1-(9-anthryl)ethane-1,2-diol ((R)-10): [a]D =
À5.71 (c=3.12 in CHCl3); 1H NMR (250.17 MHz, CDCl3): d=3.27 (s,
3H), 3.37 (s, 3H), 4.39 (dd, J=3.7 Hz, 12.2 Hz, 1H), 4.62 (s, 1H), 4.73 (s,
1H), 5.15 (dd, J=10.0 Hz, 12.2 Hz, 1H), 7.48 (dd, J=3.7 Hz, 10.0 Hz,
1H), 7.01–7.42 (m, 13H), 7.91–7.94 (m, 2H), 8.30–8.38 ppm (m, 3H);
13C NMR (62.83 MHz, CDCl3): d=57.7, 57.8, 65.8, 71.6, 82.8, 82.8, 125.2,
125.8, 127.6, 127.8, 128.9, 129.0, 129.4, 129.3, 129.5, 130.1, 130.2, 131.7,
135.9, 136.4, 170.2, 170.9 ppm; MS (EI): m/z: 534 [M+].
Bis-(R)-MPA ester of (E)-3-benzyloxyimine-3-deoxy-1,2-O-isopropyli-
den-a-d-glucofuranose [(R)-14]: [a]D =+107.09 (c=0.31 in CHCl3);
1H NMR (250.17 MHz, CDCl3): d=1.28 (s, 3H), 1.31 (s, 3H), 3.35 (s,
3H), 3.38 (s, 3H), 4.17 (dd, J=4.7 Hz, 11.7 Hz, 1H), 4.34 (dd, J=7.0 Hz,
11.7 Hz, 1H), 4.45 (d, J=4.1 Hz, 1H), 4.48 (s, 1H), 4.55 (brs, 1H), 4.68
(s, 1H), 4.77 (d, J=4.6 Hz, 1H), 5.06 (d, J=12 Hz, 1H), 5.12 (d, J=
12 Hz, 1H), 5.30–5.37 (m, 1H), 7.19–7.38 ppm (m, 15H); 13C NMR
(62.83 MHz, CDCl3): d=27.4, 57.5, 62.0, 72.0, 74.2, 76.1, 82.2, 82.3, 82.4,
104.6, 113.4, 127.4, 127.5, 127.7, 127.8, 128.3, 128.6, 128.9, 129.0, 129.1,
136.0, 136.3, 137.7, 155.9, 169.3, 170.2 ppm; MS (EI): m/z: 620 [M+].
Bis-(S)-MPA ester of (R)-1-(9-anthryl)ethane-1,2-diol ((S)-10): [a]D =
+98.78 (c=0.008 in CHCl3); 1H NMR (250.17 MHz, CDCl3): d=3.27 (s,
3H), 3.32 (s, 3H), 4.47 (s, 1H), 4.63 (dd, J=5.0 Hz, 12.2 Hz, 1H), 4.68
(dd, J=8.8 Hz, 12.2 Hz, 1H), 4.78 (s, 1H), 7.65 (dd, J=5.0, 8.8 Hz, 1H),
7.26–7.56 (m, 1H), 7.26–7.56 (m, 13H), 7.98–8.01 (m, 2H), 8.46–8.51 ppm
(m, 3H); 13C NMR (62.83 MHz, CDCl3): d=57.8, 57.9, 65.9, 71.3, 82.4,
82.9, 125.4, 126.0, 127.6, 127.8, 129.0, 129.1, 129.2, 129.8, 130.2, 130.4,
136.4, 136.7, 170.5, 170.9 ppm; MS (EI): m/z: 534 [M+].
Bis-(S)-MPA ester of (E)-3-benzyloxyimine-3-deoxy-1,2-O-isopropyli-
den-a-d-glucofuranose ((S)-14): [a]D =+188.40 (c=0.26 in CHCl3);
1H NMR (250.17 MHz, CDCl3): d=1.36 (s, 3H), 1.42 (s, 3H), 3.29 (s,
3H), 3.33 (s, 3H), 3.97 (dd, J=8.2 Hz, 12.3 Hz, 1H), 4.25 (dd, J=3.5 Hz,
12.3 Hz, 1H), 4.48 (s, 1H), 4.72 (s, 1H), 4.81 (d, J=2.3 Hz, 1H), 5.01 (d,
J=3.5 Hz, 1H), 5.13 (d, J=12.3 Hz, 1H), 5.17 (d, J=12.3 Hz, 1H), 5.38–
5.43 (m, 1H), 5.47 (d, J=4.1 Hz, 1H), 7.23–7.41 ppm (m, 15H);
13C NMR (62.83 MHz, CDCl3): d=27.4, 57.5, 62.2, 72.1, 74.1, 76.1, 82.2,
82.6, 104.7, 104.8, 109.3, 113.7, 127.1, 127.2, 127.3, 127.4, 127.5, 127.8,
128.2, 128.4, 128.6, 128.8, 128.9, 129.0, 129.1, 137.5, 155.9, 169.9,
170.2 ppm; MS (EI): m/z: 620 [M+].
Bis-(R)-MPA ester of (R)-3,3-difluoroheptane-1,2-diol ((R)-11): [a]D =
À88.85 (c=1.22 in CHCl3); 1H NMR (250.17 MHz, CDCl3): d=0.73 (t,
J=7.1 Hz, 3H), 0.94–1.08 (m, 2H), 1.10–1.22 (m, 2H), 1.23–1.25 (m,
2H), 3.39 (s, 3H), 3.40 (s, 3H), 4.35 (dd, J=7.3 Hz, 12.4 Hz, 1H), 4.48
(ddd, J=1.2, 3.1 Hz, 12.2 Hz, 1H), 4.68 (s, 1H), 4.70 (s, 1H), 5.25 (dddd,
J=1.6, 4.4, 7.5 Hz, 13.5 Hz, 1H), 7.33–7.42 ppm (m, 10H); 13C NMR
(62.83 MHz, CDCl3): d=14.1, 22.6, 23.5, 33.1, 33.5, 33.8, 57.8, 57.9, 61.8,
70.8, 71.2, 71.6, 82.4, 82.8, 127.4, 127.6, 129.0, 129.1, 129.2, 129.3, 136.1,
136.2, 170.0, 170.5 ppm; MS (EI): m/z: 464 [M+].
Bis-acetate ester of (S)-propanediol (15): [a]D =À14.7 (c=0.15 in
CH3OH); 1H NMR (250.17 MHz, CDCl3): d=1.25 (d, J=6.6 Hz, 3H),
2.06 (s, 3H), 2.08 (s, 3H), 4.05 (dd, J=6.7 Hz, 11.9 Hz, 1H), 4.17 (dd, J=
3.6 Hz, 11.9 Hz, 1H), 5.07–5.19 ppm (m, 1H); 13C NMR (62.83 MHz,
CDCl3): d=16.4, 20.8, 21.2, 66.1, 68.2, 170.5, 170.8 ppm; MS (EI): m/z:
160 [M+].
Bis-(R)-MPA ester of (R)-3,3-difluoroheptane-1,2-diol ((S)-11): [a]D =
+126.74 (c=1.04 in CHCl3); 1H NMR (250.17 MHz, CDCl3): d=0.84 (t,
J=7.1 Hz, 3H), 1.19–1.28 (m, 2H), 1.30–1.43 (m, 2H), 1.55–1.76 (m,
2H), 3.33 (s, 6H), 3.98 (dd, J=8.2 Hz, 12.1 Hz, 1H), 4.60 (dd, J=2.4 Hz,
11.9 Hz, 1H), 4.42 (s, 1H), 4.63 (ddd, J=0.9, 2.8 Hz, 11.9 Hz, 1H), 4.81
(s, 1H), 5.33–5.46 (m, 1H), 7.24–7.48 ppm (m, 10H); 13C NMR
(62.83 MHz, CDCl3): d=14.0, 22.4, 23.3, 32.6, 32.9, 57.7, 61.7, 70.1, 71.5,
82.4, 82.6, 127.6, 127.7, 129.1, 129.3, 129.5, 135.9, 136.2, 169.6, 170.7 ppm;
MS (EI): m/z: 464 [M+].
(R)-MPA ester of (S)-1-acetoxy-2-propanol ((R)-16): [a]D =À36.92 (c=
0.26 in CH3OH); 1H NMR (250.17 MHz, CDCl3): d=1.33 (d, J=6.7 Hz,
3H), 1.99 (S, 3H), 3.42 (s, 3H), 4.03 (dd, J=7.3 Hz, 11.9 Hz, 1H), 4.18
(dd, J=3.3 Hz, 11.8 Hz, 1H), 4.77 (S, 1H), 5.14–5.25 (m, 1H), 7.33–
7.46 ppm (m, 5H); 13C NMR (62.83 MHz, CDCl3): d=16.0, 20.6, 57.3,
65.8, 66.2, 69.1, 82.6, 127.1, 127.2, 128.5, 128.6, 128.7, 136.1, 170.1,
170.6 ppm; MS (EI): m/z: 266 [M+].
Bis-(R)-MPA ester of (S)-3-chloropropane-1,2-diol ((R)-12): [a]D =
1
+66.55 (c=2.92 in CHCl3); H NMR (250.17 MHz, CDCl3): d=3.25 (dd,
J=5.6 Hz, 11.6 Hz, 1H), 3.32 (dd, J=6.0 Hz, 11.5 Hz, 1H), 3.39 (s, 3H),
3.40 (s, 3H), 4.24 (dd, J=5.6 Hz, 11.9 Hz, 1H), 4.48 (dd, J=4.1 Hz,
12.2 Hz, 1H), 4.64 (s, 1H), 4.74 (s, 1H), 5.09–5.18 (m, 1H), 7.31–
7.44 ppm (m, 10H); 13C NMR (62.83 MHz, CDCl3): d=42.1, 57.7, 57.7,
62.9, 71.4, 78.0, 82.4, 82.6, 127.5, 127.6, 127.8, 129.1, 129.1, 129.2, 129.3,
136.2, 136.3, 170.2, 170.4 ppm; MS (EI): m/z: 406 [M+].
(S)-MPA ester of (S)-1-acetoxy-2-propanol ((S)-16): [a]D =+52 (c=0.32
in CH3OH); 1H NMR (250.17 MHz, CDCl3): d=1.27 (d, J=6.4 Hz, 3H),
1.79 (s, 3H), 3.42 (s, 3H), 3.97 (dd, J=7.3 Hz, 11.9 Hz, 1H), 4.02 (dd, J=
3.9 Hz, 11.9 Hz, 1H), 4.76 (s, 1H), 5.13–5.26 (m, 1H), 7.32–7.46 ppm (m,
5H); 13C NMR (62.83 MHz, CDCl3): d=16.3, 20.3, 57.2, 65.7, 66.4, 67.8,
68.9, 82.3, 82.4, 127.1, 127.2, 128.5, 128.6, 128.7, 136.2, 170.1, 170.5 ppm;
MS (EI): m/z: 266 [M+].
Bis-(S)-MPA ester of (S)-3-chloropropane-1,2-diol ((S)-12): [a]D =À73.96
(c=8.24, CHCl3); 1H NMR (250.17 MHz, CDCl3): d=3.33 (s, 3H), 3.36
(s, 3H), 3.44 (dd, J=5.4 Hz, 11.9 Hz, 1H), 3.52 (dd, J=5.4 Hz, 11.9 Hz,
1H), 4.09 (dd, J=6 Hz, 11.9 Hz, 1H), 4.29 (dd, J=4.1 Hz, 12.1 Hz, 1H),
4.55 (s, 1H), 4.78 (s, 1H), 5.17–5.25 ppm (m, 10H); 13C NMR
(62.83 MHz, CDCl3): d=41.6, 57.7, 57.8, 62.7, 71.4, 82.5, 82.6, 127.5,
127.6, 127.8, 129.1, 129.1, 129.2, 129.3, 136.1, 136.3, 170.1, 170.5 ppm; MS
(EI): m/z: 406 [M+].
(R)-MPA ester of (S)-2-acetoxypropanol ((R)-17): [a]D =+21.5 (c=1.19
in CH3OH); 1H NMR (250.17 MHz, CDCl3): d=1.13 (d, J=6.6 Hz, 3H),
1.92 (s, 3H), 3.41 (s, 3H), 4.12 (dd, J=6.3 Hz, 11.7 Hz, 1H), 4.20 (dd, J=
3.8 Hz, 11.6 Hz, 1H), 4.78 (s, 1H), 4.97–5.09 (m, 1H), 7.26–7.46 ppm (m,
5H); 13C NMR (62.83 MHz, CDCl3) d 16.2, 20.9, 29.7, 57.3, 66.2, 66.4,
67.8, 67.9, 82.3, 82.4, 127.0, 128.5, 128.6, 135.9, 170.0, 170.1 ppm; MS (EI):
m/z: 266 [M+].
Bis-(R)-MPA ester of (Z)-3-benzyloxyimine-3-deoxy-1,2-O-isopropyli-
den-a-d-glucofuranose ((R)-13): [a]D =+52.85 (c=0.28 in CHCl3);
1H NMR (250.17 MHz, CDCl3): d=1.21 (s, 3H), 1.27 (s, 3H), 3.34 (s,
3H), 3.36 (s, 3H), 4.08 (dd, J=5.2 Hz, 11.7 Hz, 1H), 4.19 (dd, J=7.0 Hz,
11.7 Hz, 1H), 4.21 (d, J=4.7 Hz, 1H), 4.57 (s, 1H), 4.63 (s, 1H), 4.90 (d,
J=4.1 Hz, 1H), 4.94 (d, J=3.5 Hz, 1H), 5.04 (brs, 2H), 5.47–5.52 (m,
(S)-MPA ester of (S)-2-acetoxypropanol ((S)-17): [a]D =À9.5 (c=0.86 in
CH3OH); 1H NMR (250.17 MHz, CDCl3): d=1.14 (d, J=6.6 Hz, 3H),
1.88 (s, 3H), 3.42 (s, 3H), 4.11 (dd, J=6.6 Hz, 11.6 Hz, 1H), 4.18 (dd, J=
3.8 Hz, 11.9 Hz, 1H), 5.03–5.16 (m, 1H), 7.30–7.46 ppm (m, 5H);
13C NMR (62.83 MHz, CDCl3): d=16.2, 20.9, 29.4, 57.3, 66.2, 66.4, 67.8,
5520
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2005, 11, 5509 – 5522