8862
N. Batoux et al. / Tetrahedron 65 (2009) 8858–8862
6.31 (d, 1H, J¼5.6 Hz, H-1), 5.39 (d, 1H, J¼3.3 Hz, H-3), 4.83 (d, 1H,
J¼5.6 Hz, H-2), 4.29 (ABX, 2H, J¼11.2, 3.88, 6.56 Hz, H-5), 4.11 (ddd,
1H, J¼2.8, 6.1, 9.8 Hz, H-4), 1.24 (s, 9H, Piv), 1.17 (s, 9H, Piv); 13C NMR
79.6 (C-4a), 77.8 (C-4b), 77.7 (C-3b), 62.4 (C-5a), 55.9 (OCH3), 55.7
(OCH3), 27.5, 27.3, 27.2, 27.1 (Piv); HRMS (ES) m/z (MþNaþ) calcu-
lated for C22H32O7Na 431.2046, found 431.2045. IR nmax (thin film,
CHCl3) 3415, 2926, 1733, 1635, 1481, 1153.
(125 MHz, CDCl3)
d 178.3, 177.5 (C]O), 162.7 (C–CN), 132.8, 132.3
(Ph), 128.3 (Ph), 101.4 (C-1), 85.4 (C-3), 75.6 (C-2, C-4), 61.1 (C-5),
39.5, 39.1 (Piv), 27.6, 27.5, 27.5 (Piv); HRMS (ES) m/z (MþHþ) cal-
4.3.9. 1-(o-Methoxy-p-methyl)-phenyl-3,5-O-pivaloyl-
anose and 1-(o-methoxy-p-methyl)-phenyl-3,5-O-pivaloyl-
furanose (5b). Product isolated as a colourless oil as a 1:1 anomeric
mixture. 7.33 (d, 1H,
-Anomer: 1H NMR (500 MHz, CDCl3)
a
-
D
-xylofur-
culated for C20H28NO6S 410.1637, found 410.1623. IR nmax (thin film,
b-D-xylo-
20
CHCl3) 2978, 1733, 1637, 1528, 1426, 1273, 1146. [
CHCl3).
a
]
þ12 (c 0.12,
D
a
d
J¼2.0 Hz, Ph), 7.08 (dd, 1H, J¼2.5, 8.5 Hz, Ph), 6.76(d, 1H, J¼8.5 Hz,
Ph), 5.44 (d, 1H, J¼3.5 Hz, H-1), 5.35 (dd, 1H, J¼1.2, 3.5 Hz, H-3),
4.69 (dt, 1H, J¼3.5, 6.5 Hz, H-4), 4.23–4.35 (m, 2H, H-5a, H-2), 4.24
(dd, 1H, J¼6.5, 11.0 Hz, H-5b), 3.77 (s, 3H, OCH3), 3.14 (d, 1H,
J¼4.7 Hz, OH), 2.30 (s, 3H, PhCH3), 1.21 (s, 9H, 3ꢁCH3), 1.19 (s, 9H,
4.3.5. 3,5-Di-O-pivaloyl-20-ethyl-
line (2e). Product isolated as a colourless oil as a single anomer: 1H
NMR (500 MHz, CDCl3)
a-D-xylofuranoso-[1,2-d]-D
20-oxazo-
d
6.06 (d, 1H, J¼5.7 Hz, H-1), 5.19 (d, 1H,
J¼3.4 Hz, H-3), 4.56 (d, 1H, J¼5.7 Hz, H-2), 4.21 (dd, 1H, J¼6.4,
11.3 Hz, H-5), 4.17 (dd, 1H, J¼6.4, 11.3 Hz, H-50), 3.93 (ddd, 1H, J¼3.4,
6.4,11.3 Hz, H-4), 2.32 (m, 2H, CH2CH3),1.16 (t, 3H, J¼7.6 Hz, CH2CH3),
3ꢁCH3); 13C NMR (125 MHz, CDCl3)
d 178.5 (C]O), 177.5 (C]O),
154.1 (OPh), 130.6, 129.7, 128.7, 124.0, 110.4 (Ph), 79.9 (C-1), 78.2
(C-3), 76.9 (C-4), 75.9 (C-2), 62.2 (C-5), 55.9 (OCH3), 39.4, 39.2, 27.6,
27.5, 27.1 (Piv), 21.1 (CH3). HRMS (CI) m/z (MþNHþ4 ) calculated for
1.15 (s, 9H, Piv), 1.12 (s, 9H, Piv); 13C NMR (125 MHz, CDCl3)
d 176.1,
175.1 (C]O), 170.8 (C–CN), 98.7 (C-1), 82.5 (C-2), 73.3 (C-3), 720.9
(C-4), 58.9 (C-5), 37.1, 37.0 (Piv), 25.2, 25.1 (Piv), 19.5 (CH2CH3), 8.3
(CH2CH3). HRMS (ES) m/z (MþHþ) calculated for C18H30NO6
C23H38NO7 440.2648, found 440.2660. IR nmax (thin film, CHCl3)
20
3409, 2973, 1725, 1643, 1215, 1128. [
a
]
ꢂ12 (c 0.25, CHCl3).
D
356.2073, found 356.2086. IR nmax (thin film, CHCl3) 2975,1735,1641.
b
-Anomer: 1H NMR (500 MHz, CDCl3)
d
7.31 (d, 1H, J¼2.5 Hz, Ph),
20
[a]
þ9 (c 1, CHCl3).
7.02 (dd, 1H, J¼2.0, 8.0 Hz, Ph), 6.75 (d, 1H, J¼8.5 Hz, Ph), 5.15 (dd,
1H, J¼2.0, 4.5 Hz, H-3), 5.08 (d, 1H, J¼3.5 Hz, H-1), 4.58 (dt, 1H,
J¼4.5, 6.0 Hz, H-4), 4.40 (m, 2H, H-5), 4.06 (dd, 1H, J¼1.5, 3.0 Hz, H-
2), 3.82 (s, 3H, OCH3), 2.85 (s, 1H, OH), 2.28 (s, 3H, CH3), 1.18 (s, 9H,
D
4.3.6. 1-O-Phenyl-3,5-di-O-pivaloyl-
isolated as a yellow oil as a 1:1 anomeric mixture.
NMR (500 MHz, CDCl3)
a
-
D
-xylofuranose (4a). Product
-Anomer: 1H
7.33 (dd, 2H, J¼7.3, 8.7 Hz, Ph), 7.10 (d, 2H,
a
d
3ꢁCH3), 1.10 (s, 9H, 3ꢁCH3); 13C NMR (125 MHz, CDCl3)
d 178.5
J¼7.7 Hz, Ph), 7.07 (dd, 1H, J¼7.3, 5.2 Hz, Ph), 5.70 (d, 1H, J¼4.6 Hz,
H-1), 5.38 (dd, 1H, J¼5.7, 6.4 Hz, H-3), 4.69 (dt, 1H, J¼4.5, 6.5 Hz,
H-4), 4.46 (dt, 1H, J¼5.3, 7.6 Hz, H-2), 4.23 (dd, 1H, J¼4.3, 12.1 Hz,
H-5a), 4.10 (dd, 1H, J¼4.8, 12.1 Hz, H-5b), 2.94 (d, 1H, J¼7.9 Hz, OH),
(C]O), 178.0 (C]O), 154.3 (CØCH3), 129.0, 127.9, 126.9, 110.4 (Ph),
83.4 (C-1), 82.7 (C-2), 79.7 (C-3), 77.8 (C-4), 62.2 (C-5), 56.1 (OCH3),
39.2, 39.1 (Piv), 27.6, 27.2 (Piv), 21.0 (CH3); HRMS (CI) m/z (MþHþ)
calculated for C23H35O7 423.2382, found 423.2376. IR nmax (thin
20
1.25 (s, 9H, Piv), 1.22 (s, 9H, Piv); 13C NMR (125 MHz, CDCl3)
d
178.5
film, CHCl3) 3401, 2975, 1722, 1643, 1454, 1216, 1130. [
0.15, CHCl3).
a
]
ꢂ25 (c
D
(C]O),178.4 (C]O),156.6 (CØ),130.0, 129.8, 123.5, 117.5, 116.7 (Ph),
99.7 (C-1), 77.9 (C-3), 76.8 (C-2), 75.8 (C-4), 52.1 (C-5), 27.6, 27.5,
27.4 (Piv). HRMS (EI) m/z (Mþ) calculated for C21H30O7 394.1992,
Acknowledgements
found 394.1976. IR nmax (thin film, CHCl3) 3401, 2923, 1731, 1640,
20
1451. [
a
]
ꢂ13 (c 0.2, CHCl3).
D
We would like to thank QUILL, Merck KGaA for the donation of
ionic liquids and funding and EPSRC (Portfolio Partnership) grant,
MRC (Grant number G0001004) for funding.
4.3.7. 1-O-p-Methyl phenyl-3,5-di-O-pivaloyl-
Product isolated as a pale yellow oil as a 1:1 anomeric mixture.
-Anomer: 1H NMR (500 MHz, CDCl3)
a-D-xylofuranose (4b).
a
d
7.10 (d, 2H, J¼14.5 Hz, Ph),
6.98 (d, 2H, J¼14.0 Hz, Ph), 5.64 (d, 1H, J¼8.0 Hz, H-1), 5.38 (dd, 1H,
J¼3.5, 6.0 Hz, H-3), 4.69 (dt, 1H, J¼8.5, 16.5 Hz, H-4), 4.43 (dt, 1H,
J¼8.5, 12.0 Hz, H-2), 4.23–4.05 (m, 2H, H-5a,b), 2.94 (d, 1H,
References and notes
1. Gant, T. G.; Meyers, A. I. Tetrahedron 1994, 50, 2297–2360.
2. Meyers, A. I.; Temple, D. L.; Haidukewych, D.; Mihelich, E. D. J. Org. Chem. 1974,
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3. Yonehara, K.; Hashizume, T.; Mori, K.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64,
9374–9380.
J¼13.0 Hz, OH), 2.16 (s, 3H, CH3),1.25 (s, 9H, Piv),1.20 (s, 9H, Piv); 13
C
NMR (125 MHz, CDCl3)
d 178.4 (C]O), 178.5 (C]O), 168.3 (CØ),
154.4 (CØ),132.9,130.4,128.3,117.5 (Ph),100.0 (C-1), 78.0 (C-3), 76.6
(C-2), 75.7 (C-4), 62.1 (C-5), 39.3 (CH3), 27.7, 27.6, 27.5, 27.4 (Piv);
HRMS (ES-) m/z (MꢂHþ) calculated for C22H31O7 407.2070, found
4. Gosselin, G.; Bergogne, M. C.; De Rudder, J.; De Clercq, E.; Imbach, L. J. J. Med.
Chem. 1986, 29, 203–213.
5. Gordon, D. M.; Danishefsky, S. J. J. Org. Chem. 1991, 56, 3713–3715.
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J. V.; Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron 1994, 50,
799–808; (c) Takemoto, Y.; Kuraoka, S.; Hamaue, N.; Aoe, K.; Hiramatsu, H.; Iwata,
C. Tetrahedron 1996, 52, 14177–14188; (d) Peng, Y.; Feng, X.; Yu, K.; Li, Z.; Jiang, Y.;
Yeung, C.-H. J. Organomet. Chem. 2001, 619, 204–208.
407.2087. IR nmax (thin film, CHCl3) 3412, 2925, 1733, 1635, 1456.
20
[a]
ꢂ14 (c 1, CHCl3).
D
4.3.8. 1-o-Methoxyphenyl-3,5-di-O-pivaloyl-
o-methoxyphenyl-3,5-di-O-pivaloyl- -xylofuranose (5a). Product
isolated as a colourless oil as an inseparable 1:1 anomeric mixture.
1H NMR (500 MHz, CDCl3)
a-D-xylofuranose and 1-
b-D
7. Lohray, B. B. Synthesis 1992, 1035–1052.
8. Gao, Y.; Sharpless, K. B. J. Am. Chem. Soc. 1988, 110, 7538–7539.
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2009, 65, 6341–6347.
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660–669.
11. Xiao, L.-F.; Li, F.-W.; Peng, J.-J.; Xia, C.-G. J. Mol. Catal. A: Chem. 2006, 253,
265–269.
12. Barrosse-Antle, L. E.; Silvester, D. S.; Aldous, L.; Hardacre, C.; Compton, R. G.
J. Phys. Chem. C 2008, 112, 3398–3404.
13. Lever, S. D.; Papadaki, M. J. Loss Prev. Process Ind. 2005, 18, 392–396.
14. Benksim, A.; Beaupere, D.; Wadouachi, A. Org. Lett. 2004, 6, 3913–3915.
15. (a) Benksim, A.; Massoui, M.; Beaupere, D.; Wadouachi, A. Tetrahedron Lett.
2007, 48, 5087–5089; (b) Aouad, M. E.; Meslouti, A. E.; Uzan, R.; Beaupere, D.
Tetrahedron Lett. 1994, 35, 6279–6282; (c) Guiller, A.; Gagnieu, C. H.; Pacheco, H.
J. Carbohydr. Chem. 1986, 5, 153–160.
d
7.55 (d, 1H, J¼12.4 Hz, Ph), 6.37 (d, 2H,
J¼14.5 Hz, Ph), 7.24 (t, 1H, J¼13.2 Hz, Ph), 6.99 (t, 1H, J¼12.5 Hz, Ph),
6.91 (d, 2H, J¼15.8 Hz, Ph), 6.90 (dt, 1H, J¼7.9 Hz, Ph), 5.18 (dd, 1H,
J¼1.2, 3.9 Hz, H-2
a
), 5.13 (d, 1H, J¼3.3 Hz, H-1 ), 5.07 (dd, 1H, J¼2.7,
a
5.1 Hz, H-3
b
), 4.72 (d,1H, J¼5.7 Hz, H-1
b
), 4.62 (dt,1H, J¼10.2, 6.0 Hz,
), 4.43–4.37 (m, 5H, H-5
b), 3.88 (s, 3H, OCH3), 3.82 (s,
H-4a
b
), 4.53 (dd, 1H, J¼5.7, 11.4 Hz, H-4
b
a,b,
H-3
), 4.04 (dd, 1H, J¼5.7, 2.7 Hz, H-2
3H, OCH3), 3.12 (d, 1H, J¼4.7 Hz, OH), 2.84 (d, 1H, J¼4.4 Hz, OH), 1.21
(s, 9H, Piv), 1.20 (s, 9H, Piv), 1.19 (s, 9H, Piv), 1.18 (s, 9H, Piv); 13C NMR
(125 MHz, CDCl3)
(C]O), 159.8 (CØ), 156.3 (CØ), 128.8, 127.6, 126.3, 121.2, 114.2, 110.3
(Ph), 85.4 (C-1 ), 84.2 (C-2 ), 83.7 (C-3 ), 82.7 (C-1 ), 81.9 (C-2 ),
d 207.3 (CØOCH3),179.3 (C]O), 178.5 (C]O), 178.0
ˆ
¨
16. Bonhote, P.; Dias, A.; Papageorgiou, N.; Kalyanasundaram, K.; Gratzel, M. Inorg.
Chem. 1996, 35, 1168–1178.
a
a
a
b
b