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Takano et al.
H3), 2.06 (s, 3H, C(O)CH3), 2.04 (s, 3H, C(O)CH3); 13C NMR (100.62 MHz, CDCl3): d
170.5 (s, C O), 170.2 (s, C O), 146.3 (d, 3JPC = 9.2 Hz, C1), 132.4–128.7 (m, Ph), 91.4
2
2
(d, JPC = 7.4 Hz, C2), 72.1 (s, C4), 65.1 (d, JPC = 15.3 Hz, C5), 62.9 (s, C6), 37.2 (d,
1JPC = 65.9 Hz, C3), 20.8 (s, C(O)CH3), 20.6 (s, C(O)CH3); 31P NMR (161.97 MHz,
CDCl3): d 27.1; MS(Fab) m/z 415 (M++ 1).
Diphenyl(4,6-di-O-benzyl-2,3-dideoxy- -D-erythro-hex-2-enopyranosyl)-
phosphine oxide 12a; white syrup; IR (neat); n 3050, 2930, 2860, 1750, 1590, 1460,
1
1440, 1260, 1180, 1120, 1090, 1020, 800, 720 and 690 cmꢀ 1; H NMR (500.13 MHz,
CDCl3): d 7.96–7.19 (m, 20H, Ph), 6.18 (br.d, J2,3 = 10.60 Hz, 1H, H2), 6.12 (dd,
J2,3 = 10.60 Hz, J3,4 = 3.00 Hz, 1H, H3), 5.12 (dd, J12 = 2.5 Hz, JPH = 10.9 Hz, 1H,H1),
4.54 (d, Jgem = 12.0 Hz, PhCH2), 4.45 (d, Jgem = 12.0 Hz, PhCH2), 4.41 (d, Jgem = 11.7
Hz, PhCH2), 4.31 (d, Jgem = 11.7 Hz, PhCH2), 3.97–3.93 (m, 2H, H4 and H5), 3.61–3.54
(m, 2H, H6 and H6’); 13C NMR (125.76 MHz, CDCl3): d 138.2–127.6 (m, Ph, C3), 124.0
(d, 2JPC = 2.1 Hz, C2), 73.8 (d, 3JPC = 3.4 Hz, C5), 73.2 (s, PhCH2), 72.8 (d, 1JPC = 82.1
Hz, C1), 69.9 (s, PhCH2), 68.8 (s, C4), 68.7 (s, C6); 31P NMR (202.46 MHz, CDCl3): d
27.3. HRMS (Fab): Calcd for C32H32O4P: M + 1 511.2038. Found: M++ 1, m/z, 511.2037.
Diphenylphosphinoyl 4,6-di-O-benzyl-1,2,3-trideoxy- -D-erythro-hex-2-enopyra-
noside 12b; white syrup; IR (neat); n 3050, 2850, 1720, 1630, 1580, 1490, 1440, 1360,
1300, 1260, 1180, 1110, 1090, 740, 720 and 690 cmꢀ 1; 1H NMR (500.13 MHz, CDCl3):d
7.94–7.22 (m, 20H,Ph), 6.16 (ddd, J1,2 = 2.60 Hz, J2,3 = 10.5 Hz, JPH = 4.25 Hz, 1H, H2),
6.01–5.99 (m, 1H, H3), 5.14 (dd, J1,2 = 2.60 Hz, JPH = 9.05 Hz, 1H, H1), 4.57–4.34 (m,
4H, PhCH2), 3.77–3.71 (m, 2H, H4, H6), 3.66–3.57 (m, 2H, H6’, H5); 13C NMR (125.76
MHz, CDCl3): d 138.4–127.5 (m, Ph), 129.3 (d, 3JPC = 9.3 Hz, C3), 123.3 (d, 2JPC = 5.3
Hz, C2), 76.5 (d, 3JPC = 7.3 Hz, C5), 75.0 (d, 1JPC = 91.9 Hz, C1), 73.3 (s, PhCH2), 71.2 (s,
PhCH2), 69.6 (d, 4JPC = 2.3 Hz, C4), 69.4 (s, C6); 31P NMR (202.46 MHz, CDCl3): d 27.8.
HRMS: Calcd for C32H31O4P: M, 510.1960. Found: M+, m/z, 510.1957.
1,5-anhydro-4,6-di-O-benzyl-2,3-dideoxy-3-diphenylphosphinoyl-D-ribo-hex-1-
enitol 13; white crystals: mp 126–128.5ꢀC; IR (KBr); n 3050, 2900, 1640, 1440, 1370,
1
1330, 1260, 1210, 1170, 1100, 920, 890, 840,and 690 cmꢀ 1; H NMR (500.13 MHz,
CDCl3):d 7.82–7.79, 7.42–7.11, 6.79–6.78 (m, 20H, Ph), 6.48–6.46 (m, 1H, H1),
4.85–4.82 (m, 1H, H5), 4.50 (d, Jgem = 12.1 Hz, 1H, PhCH2), 4.44 (d, 1H, Jgem = 12.1
Hz, PhCH2), 4.30–4.27 (m, 1H, H2), 4.27 (d, Jgem = 12.1 Hz, 1H, PhCH2), 4.24–4.19
(m, 1H, H4), 4.14 (d, Jgem = 11.3 Hz, 1H, PhCH2), 3.78 (dd, Jgem = 10.7 Hz, J5,6 = 3.8
Hz, 1H, H6), 3.67 (dd, Jgem = 10.7 Hz, J5,6’ = 2.8 Hz, 1H, H6’), 3.59–3.55 (m, 1H,
3
H3); 13C NMR (125.77 MHz, CDCl3): d 145.9 (d, JPC = 9.8 Hz, C1), 138.1, 137.4,
2
134.6, 134.1, 133.8, 133.3, 131.3–130.9, 128.5–125.9 (m, Ph), 92.8 (d, JPC = 6.8 Hz,
3
C2), 74.5 (d, JPC = 1.9 Hz, C5), 73.5 (s, PhCH2), 72.73 (d, JPC = 6.7 Hz, C4), 72.72
2
1
(s, PhCH2), 68.7 (s,C6), 37.2 (d, JPC = 72.4 Hz, C3); 31P NMR (202.46 MHz,CDCl3):
d 27.7. HRMS: Calcd for C32H31O4P: M, 510.1960. Found: M+, m/z, 510.1958.
Acid catalyzed hydrolysis of 3. To a solution of 3 (2.07 g, 5 mmol) in methanol
(20 ml) was added one-drop of 10% hydrochloric acid and the resulting mixture was
refluxed for 18 h. After cooling, the solvent was removed in vacuo, and the residue was
extracted with dichloromethane. The organic layer was washed with brine, dried over
anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was