V. Aucagne et al. / Tetrahedron 60 (2004) 1817–1826
1823
4.2.11. 1,2-Dideoxy-3,4-O-isopropylidene-1-phenylthio-
5,6-di-O-pivaloyl-D-ribo-hex-1-enitols (13). Eluent:
J3–4¼7.7 Hz, H-3), 6.07 (dd, 1H, J1–2¼9.5 Hz, H-2), 6.49
(dd, 1H, H-1); 7.20–7.41 (m, 5H, HAr). 13C NMR: E
isomer: d 24.4, 25.5, 26.7, 27.1 (4pMe), 67.0 (C-7), 70.6
(C-5), 74.7 (C-3), 76.2 (C-6), 76.5 (C-4), 108.9, 109.5
(2pCIV-iPrd), 127.2 (C-2), 128.1 (CAr), 128.2 (C-1), 129.3,
129.6, 135.0 (CAr),; Z isomer: d 24.6, 25.4, 26.8, 26.9
(4pMe), 67.2 (C-7), 70.7 (C-5), 76.2 (C-6), 76.9 (C-4), 78.6
(C-3), 108.7, 109.5 (2pCIV-iPrd), 126.5 (C-2), 130.4 (C-1),
127.4, 129.3, 130.6, 134.4 (CAr). HRMS: C19H26O5S calcd
366.1501; found 366.1511.
1
petroleum ether–ethyl acetate 92:8; yellow oil. H NMR
(CDCl3): E isomer: d 1.17 (s, 9H, Me3C), 2.21 (s, 3H,
Me2C), 1.26 (s, 3H, Me2C), 1.37 (s, 3H, Me2C), 4.12 (dd,
1H, J6a–6b¼12.2 Hz, J6a–5¼5.3 Hz, H-6b), 4.27–4.38 (m,
1H, H-4), 4.45–4.57 (m, 1H, H-6a), 4.71 (dd, 1H,
J2–3¼7.5 Hz, J3–4¼6.3 Hz, H-3), 4.96–5.05 (m, 1H,
H-5), 5.66 (dd, 1H, J1–2¼14.9 Hz, H-2), 6.50 (d, 1H,
H-1), 7.20–7.48 (m, 5H, HAr); Z isomer: d 1.17 (s, 9H,
Me3C), 2.21 (s, 9H, Me2C), 1.41 (s, 3H, Me2C), 1.51 (s, 3H,
Me2C), 4.12 (dd, 1H, J6a–6b¼12.2 Hz, J6a–5¼5.3 Hz,
H-6b), 4.27–4.38 (m, 1H, H-4), 4.52 (dd, J6a–5¼2.4 Hz,
H-6a), 5.15 (m, 2H, H-3, H-5), 5.78 (dd, 1H, J1–2¼9.6 Hz,
H-2), 6.45 (dd, 1H, J1–3¼0.6 Hz, H-1), 7.20–7.48 (m, 5H,
HAr). 13C NMR (CDCl3): E isomer: d 25.5 (Me2C), 27.2
(2pMe3C), 27.8 (Me2C), 38.9 (2pCMe3), 63.2 (C-6), 69.3
(C-5), 75.5 (C-4), 78.2 (C-3), 109.2 (CIV-iPrd), 124.5 (C-2),
127.4, 129.5, 130.1 (CAr), 129.5 (C-1), 134.2 (CAr); Z
isomer: d 25.5 (Me2C), 27.2 (2pMe3C), 27.8 (Me2C), 38.9
(2pCMe3), 63.5 (C-6), 69.5 (C-5), 74.3 (C-3), 75.7 (C-4),
109.4 (CIV-iPrd), 124.9 (C-2), 127.2, 129.3, 129.8 (CAr),
130.8 (C-1), 135.1 (CAr). HRMS: C25H36O6S calcd
464.2232; found 464.2221.
4.2.14. 1,2-Dideoxy-3,4,5,7-di-O-isopropylidene-1-
methylthio-D-manno-hept-1-enitols (4e). Prepared from
2,3:4,6-di-O-isopropylidene-D-mannopyranose 3e.26 Eluent:
1
petroleum ether–ethyl acetate 85:15; yellow oil. H NMR
(CDCl3): E isomer: d 1.38, 1.42, 1.48, 1.53 (4s, 4£3H, Me2C),
2.27 (s, 3H, SMe), 3.52–3.69 (m, 2H, H-5, H-7b), 3.85–3.98
(m, 2H, H-6, H-7a), 4.39 (dd, 1H, J3–4¼7.0 Hz, J4–5¼1.3 Hz,
H-4), 4.79 (dd, 1H, J2–3¼6.7 Hz, H-3), 5.76 (dd, 1H,
J1–2¼14.9 Hz, H-2), 6.17 (dd, 1H, H-1); Z isomer: d 1.39,
1.40, 1.42, 1.53 (4s, 4£3H, Me2C), 2.31 (s, 3H, SMe), 2.92–
3.05 (m, 1H, OH), 3.43 (dd, 1H, J5–6¼8.9 Hz, J4–5¼1.5 Hz,
H-5), 3.55–3.67 (m, 1H, H-7b), 3.78–3.93 (m, 2H, H-6,
H-7a), 4.48 (dd, 1H, J3–4¼7.2 Hz, H-4), 5.12 (ddd, 1H,
J2–3¼7.7 Hz, J1–3¼1.3 Hz, H-3,), 5.76 (dd, 1H,
J1–2¼9.8 Hz, H-2), 6.17 (dd, 1H, H-1). 13C NMR: d E
isomer: 14.3 (MeS), 21.1, 26.0, 26.4, 28.6 (4pMe), 60.5 (C-7),
62.7 (C-6), 73.0 (C-5), 75.7 (C-4), 79.0 (C-3), 98.6, 109.3
(2pCIV-iPrd), 118.8 (C-2), 131.9 (C-1); Z isomer: d 17.5
(MeS), 19.2, 26.0, 26.4, 28.6 (4pMe), 62.8 (C-6), 64.9 (C-7),
73.0 (C-5), 74.7 (C-3), 75.1 (C-4), 98.6, 109.4 (2pCIV-iPrd),
124.5 (C-2), 130.9 (C-1). HRMS: C14H24O5S calcd 304.1344;
found 304.1331.
4.2.12. 1,2-Dideoxy-3,4,6,7-di-O-isopropylidene-1-
methylthio-D-manno-hept-1-enitols (4d). Prepared from
commercial 2,3:5,6-di-O-isopropylidene-D-mannofuranose
3d. Eluent: petroleum ether–ethyl acetate 85:15; yellowish
1
oil. H NMR (CDCl3): E isomer: d 1.35, 1.40, 1.52 (3s,
4£3H, Me2C), 2.22 (d, 1H, OH, JOH-5¼7.4 Hz), 2.29 (s, 3H,
SMe), 3.45 (ddd, 1H, J5–6¼7.4 Hz, J4–5¼1.4 Hz, H-5),
3.95–4.12 (m, 3H, H-6, H-7a, H-7b), 4.34 (dd, 1H,
J3–4¼7.5 Hz, H-4), 4.78 (dd, 1H, J2–3¼8.5 Hz, H-3), 5.62
(dd, 1H, J1–2¼14.9 Hz, H-2), 6.47 (dd, 1H, H-1); Z isomer:
d 1.35, 1.40, 1.42, 1.53 (4s, 4£3H, Me2C), 2.13 (d, 1H, OH,
JOH-5¼7.4 Hz), 2.31 (s, 3H, SMe), 3.40 (ddd, 1H,
J5–6¼7.6 Hz, J4–5¼1.2 Hz, H-5), 3.95–4.12 (m, 3H, H-6,
H-7a, H-7b), 4.44 (dd, 1H, J3–4¼7.5 Hz, H-4), 5,11 (ddd,
1H, J2–3¼8.7 Hz, J1–3¼0.9 Hz, H-3), 5.83 (dd, 1H,
J1–2¼9.6 Hz, H-2), 6.22 (dd, 1H, H-1). 13C NMR: E
isomer: d 14.4 (MeS), 24.5, 25.3, 26.7, 26.9 (4pMe), 67.1
(C-7), 70.7 (C-5), 76.2 (C-6), 76.2 (C-4), 79.2 (C-3), 108.2,
109.4 (2pCIV-iPrd), 119.4 (C-2), 132.4 (C-1); Z isomer: 17.5
(MeS), 24.4, 25.4, 26.6, 26.9 (4pMe), 66.8 (C-7), 70.4 (C-5),
74.7 (C-3), 76.1 (C-6), 76.6 (C-4), 108.6, 109.3 (2pCIV-
iPrd), 124.7 (C-2), 131.5 (C-1). HRMS: C14H24O5S calcd
304.1344; found 304.1349.
4.2.15. 1,2-Dideoxy-3,4,5,7-di-O-isopropylidene-1-
phenylthio-D-manno-hept-1-enitols (5e). Reaction of 3e
with phosphorane 2 afforded 5e contaminated with side-
products including triphenylphosphine oxide; the crude
mixture was first acetylated under standard procedure to
give pure 6-O-acetyl-1,2-dideoxy-3,4,5,7-di-O-isopropyl-
idene-1-phenylthio-D-manno-hept-1-enitols 14. Eluent:
petroleum ether–ethyl acetate 90:10; colorless oil. 1H
NMR (C6D6): E isomer: d 1.24 (s, 3H, Me2C), 1.29 (s,
3H, Me2C), 1.35 (s, 3H, Me2C), 1.60 (s, 3H, Me2C), 1.59 (s,
3H, CH3CO), 3.54 (dd, 1H, J7a–7b¼12.0 Hz, J6–7b¼6.0 Hz,
H-7b), 3.70 (dd, 1H, J4–5¼1.3 Hz, J5–6¼8.5 Hz, H-5), 4.07
(dd, 1H, J6–7a¼4.5 Hz, H-7a), 4.19 (dd, 1H, J3–4¼7.2 Hz,
H-4), 4.59 (dd, 1H, J2–3¼7.9 Hz, H-3), 5.34 (ddd, 1H, H-6),
6.12 (dd, 1H, J1–2¼15.1 Hz, H-2), 6.32 (d, 1H, H-1), 7,22–
7,42 (m, 5H, HAr); Z isomer: d 1.23 (s, 3H, Me2C), 1.29 (s,
3H, Me2C), 1.30 (s, 3H, Me2C), 1.55 (s, 3H, Me2C), 1.59 (s,
3H, CH3CO), 3.50 (dd, 1H, J7a–7b¼11.9 Hz, J6–7b¼6.2 Hz,
H-7b), 3.70 (dd, 1H, J4–5¼1.0 Hz, J5–6¼8.0 Hz, H-5), 4.02
(dd, 1H, J6–7a¼5.0 Hz, H-7a), 4.44 (dd, 1H, J3–4¼7.2 Hz,
H-4), 5.25 (ddd, 1H, H-6), 5.35 (dd, 1H, J2–3¼6.2 Hz, H-3),
6.09 (dd, 1H, J1–2¼9.5 Hz, H-2), 6.15 (d, 1H, H-1), 7,22–
7,42 (m, 5H, HAr). 13C NMR (C6D6): E isomer: d 20.5,
21.0, 26.1, 26.8 (Me2C), 62.4 (C-7), 68.0 (C-6), 70.2 (C-5),
76.9 (C-4), 78.6 (C-3), 99.7, 109.7 (CIV-iPrd), 127.36 (CAr),
125.0 (C-2), 126.3 (C-1), 129.5, 130.8, 132.4 (CAr), 169.5
(CO); Z isomer: d 20.5, 21.0, 26.7, 27.0 (Me2C), 62.4 (C-6),
67.6 (C-7), 70.3 (C-5), 75.2 (C-3), 76.4 (C-4), 99.6, 109.9
(CIV-iPrd), 126.1 (C-2), 127.1, 129.5, 129.6 (CAr), 129.9
4.2.13. 1,2-Dideoxy-3,4,6,7-di-O-isopropylidene-1-phe-
nylthio-D-manno-hept-1-enitols (5d). Prepared from com-
mercial 2,3:5,6-di-O-isopropylidene-D-mannofuranose 3d.
Eluent: petroleum ether–ethyl acetate 85:15; yellow oil. 1H
NMR (CDCl3): E isomer: d 1.35, 1.40, 1.51 (3s, 4£3H,
Me2C), 2.14 (d, 1H, OH, JOH-5¼7.7 Hz), 3.45 (ddd, 1H,
J5–6¼7.7 Hz, J4–5¼1.5 Hz, H-5), 3.95–4.15 (m, 3H, H-6,
H-7a, H-7b), 4.36 (dd, 1H, J3–4¼7.3 Hz, H-4), 4.78 (dd, 1H,
J2–3¼8.3 Hz, H-3), 6.02 (dd, 1H, J1–2¼15.1 Hz, H-2), 6.57
(dd, 1H, H-1); 7.20–7.41 (m, 5H, HAr); Z isomer: d 1.36),
1.42, 1.44, 1.55 (4s, 4£3H, Me2C), 2.18 (d, 1H, OH,
JOH-5¼7.7 Hz), 3.44 (ddd, 1H, J5–6¼7.7 Hz, J4–5¼0.8 Hz,
H-5), 3.97–4.15 (m, 3H, H-6, H-7a, H-7b), 4.51 (dd, 1H,
J3–4¼7.7 Hz, H-4), 5.24 (ddd, 1H, J2–3¼7.8 Hz,