1802
O. Schulze et al. / Carbohydrate Research 339 (2004) 1787–1802
(s, 3H, OMe0), 3.45 (dd, 1H, H-5exo), 3.66 (dd, 1H, H-2),
4.21 (dd, 1H, H-3), 5.24 (d, 1H, H-1), 5.40 (ddd, 1H, H-
4) ppm; J1;2 2.2, J2;3 6.7, J3;4 6.4, J4;5-endo 2.8, J4;5-exo 6.0,
J5-endo;5-exo 9.5 Hz; 13C NMR (101 MHz, CDCl3): d 18.07
(C-5), 33.59 (C-3), 55.44 (OMe0), 58.41 (OMe), 82.18 (C-
4), 84.87 (C-2), 107.89 (C-1) ppm; J5;Se 12.9, J3;Se 21.3 Hz;
EIMS: m=z (%) 224 (28) [Mþꢀ], 164 (63)
[Mþꢀ)HCO2Me], 162 (31) [Mþꢀ)2OMe], 135 (19), 133
(100) [Mþꢀ)HCO2Me, –OMe], 131 (49), 130 (22)
[Mþꢀ)H2C@Se], 101 (44), 84 (47), 71 (42), 69 (43), 45
(59), 41 (62), 39 (41); HRMS Calcd for C7H12O3Se: m=z
223.9952. Found: m=z 223.9922.
Laupichler, L.; Rollin, P.; Thiem, J. Liebigs Ann. Chem.
ꢀ
1993, 343–350; (e) Branalt, J.; Kvarnstrom, I.; Classon, B.;
Samuelsson, J. J. Org. Chem. 1996, 61, 3604–3610; (f)
€
ꢁ
Moravkova, J.; Rollin, P.; Lorin, C.; Gardon, V.;
Capkova, J.; Mazac, J. J. Carbohydr. Chem. 1997, 16,
ꢂ
ꢁ
ꢁꢂ
113–127.
2. Schulze, O.; Voss, J.; Adiwidjaja, G. Synthesis 2001, 229–
234.
3. Adiwidjaja, G.; Brunck, J.-S.; Polchow, K.; Voss, J.
Carbohydr. Res. 2000, 325, 237–244.
4. Schulze, O.; Bruns, S.; Voss, J.; Adiwidjaja, G. Carbohydr.
Res. 2000, 329, 781–790.
5. Preliminary note: Voss, J.; Schulze, O.; Olbrich, F.;
Adiwidjaja, G. Phosphorus Sulfur Silicon 1997, 120–121,
389–390.
6. (a) Yuasa, H.; Kajimoto, T.; Wong, C.-H. Tetrahedron
Lett. 1994, 35, 8243–8246; (b) Yuasa, H.; Hashimoto, H.
3.15. Methyl 3,5-anhydro-2-O-methyl-3,5-diseleno-a-D-
lyxofuranoside (31)
ꢁ
Rev. Heteroat. Chem. 1998, 19, 35–65; (c) Bozo, E.; Boros,
ꢁ
S.; Kuczmann, J. Carbohydr. Res. 2000, 329, 525–528.
7. (a) Hirota, K.; Kitade, Y.; Tomishi, T.; Maki, Y.;
De Clercq, E. J. Chem. Soc., Perkin Trans. 1 1988,
2233–2241; (b) Yoshimura, Y.; Kitano, K.; Yamada, K.;
Satoh, H.; Watanabe, M.; Miura, S.; Sakata, S.; Sasaki,
T.; Matsuda, A. J. Org. Chem. 1997, 62, 3140–3152; (c)
Singh, S. K.; Kumar, R.; Wengel, J. J. Org. Chem. 1998,
63, 6078–6079.
8. (a) Yoshikawa, M.; Murakami, T.; Shimada, H.; Mat-
suda, H.; Yamahara, J.; Tanabe, G.; Muraoka, O.
Tetrahedron Lett. 1997, 38, 8367–8370; (b) Yuasa, H.;
Takada, J.; Hashimoto, H. Tetrahedron Lett. 2000, 41,
6615–6618; (c) Ghavami, A.; Johnston, B. D.; Pinto, B. M.
J. Org. Chem. 2001, 66, 2312–2317.
1H NMR (500 MHz, CDCl3): d 3.42 (s, 3H, OMe), 3.46
(s, 3H, OMe0), 3.47 (dd, 1H, H-5endo), 3.74 (dd, 1H, H-
5
exo), 3.90 (dd, 1H, H-2), 4.56 (dd, 1H, H-3), 5.07 (d, 1H,
H-1), 5.45 (ddd, 1H, H-4) ppm; J1;2 2.8, J2;3 6.4, J3;4 5.2,
J4;5-endo 4.0, J4;5-exo 2.8, J5-endo;5-exo 12.0 Hz; 13C NMR
(101 MHz, CDCl3): d 38.97 (C-5), 55.86 (OMe), 58.02
(C-3), 59.03 (OMe0), 86.10 (C-2), 88.36 (C-4), 108.08 (C-
1) ppm.
4. Supplementary material
9. Wirsching, J. Ph.D. thesis, University of Hamburg, 2000,
to be published elsewhere.
Full crystallographic details, excluding structure fea-
tures, have been deposited with the Cambridge Crys-
tallographic Data Centre. These data may be obtained,
on request, from the CCDC, 12 Union Road, Cam-
bridge CB2 1EZ, UK. Tel.: +44 1223 336408, fax: +44
CCDC 142684 (4a), 142680 (4b), 142683 (19), 142681
(22a), 142682 (22b), 142689 (24) and 142686 (29). For
convenience, the central atoms in the ORTEP plots
(Figs. 1–3) are numbered according to the common
carbohydrate nomenclature, which differs from the
numberingin the CCDC files!
10. (a) Collins, P.; Ferrier, R. Monosaccharides. Their Chem-
istry and Their Roles in Natural Products; Wiley: Chich-
ester, 1995; pp 194–196; (b) Lehmann, J. Kohlenhydrate.
Chemie und Biologie, 2nd ed.; Thieme: Stuttgart, New
York, 1996; pp 115–116; (c) Miljkovic, M.; Gligorijewic,
ꢂ
M.; Glisin, D. J. Org. Chem. 1974, 39, 3223–3226; (d)
Richardson, A. C. Carbohydr. Res. 1969, 10, 395–402, and
references cited therein.
~
11. (a) Fernandez-Bolanos, J. G.; Al-Masoudi, N. A. L.;
Maya, I. Adv. Carbohydr. Chem. Biochem. 2001, 57, 21–98,
ꢁ
ꢁ
and references cited therein; (b) Bozo, E.; Medgyes, A.;
Boros, S.; Kuczmann, J. Carbohydr. Res. 2000, 329, 25–40,
and references cited therein.
ꢁ
12. Thome, M. A.; Giudicelli, M. B.; Picq, D.; Anker, D.
J. Carbohydr. Chem. 1991, 10, 923–926.
13. Adiwidjaja, G.; Schulze, O.; Voss, J.; Wirsching, J.
Carbohydr. Res. 2000, 325, 107–119.
14. Becker, H. Organikum: Organisch-chemisches Grund-
praktikum. 19th ed.; Johann Ambrosius Barth: Leipzig,
1993; pp 659–681.
Acknowledgements
We thank the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie for their financial
€
support. O.S. thanks the Universitat Hamburgfor a
Graduate Scholarship.
15. Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi,
A.; Moliterni, A. G. G.; Burla, M. C.; Polidori, G.;
Camalli, M.; Spagna, R. SIR97; A Package for Crystal
Structure Solution by Direct Methods and Refinement,
Bari, Perugia, Rome, Italy, 1997.
16. Sheldrick, G. M. SHELXL-97 Program for Crystal Struc-
€
ture Refinement, University of Gottingen, Gottingen,
Germany, 1997.
€
References
17. Spek, A. L. PLATON; A Multipurpose Crystallographic
Tool, Utrecht University, Utrecht, The Netherlands, 1999.
18. Baker, B. R.; Schaub, R. E.; Williams, J. H. J. Am. Chem.
Soc. 1955, 77, 7–12.
1. (a) Mitsunobu, O. Synthesis 1981, 1–28; (b) Hughes, D. L.
Org. React. 1992, 42, 335–656; (c) Kawai, S. H.; Chin, J.;
Just, G. Carbohydr. Res. 1991, 211, 245–260; (d) Dancy, I.;