Flexibility in the partial reduction of 2,5-disubstituted pyrroles: Application to the synthesis of DMDP

Organic Letters

Volumn 5, Issue 7, 2003, Pages 999-1002

  Donohoe, Timothy J ^a   Headley, Catherine E ^a,b   Cousins, Rick P C ^c   Cowley, Andrew ^a  

^a UNIVERSITY OF OXFORD   (United Kingdom)

^b UNIVERSITY OF MANCHESTER   (United Kingdom)

^c GLAXOSMITHKLINE   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

BIS(HYDROXYMETHYL)DIHYDROXYPYRROLIDINE; GLYCOSIDASE INHIBITOR; PYRROLE DERIVATIVE; UNCLASSIFIED DRUG; 2,5-DIHYDROXYMETHYL-3,4-DIHYDROXYPYRROLIDINE; 3,4 DIHYDROXY 2,5 BIS(HYDROXYMETHYL)PYRROLIDINE; ALKALOID; DRUG DERIVATIVE; ENZYME INHIBITOR; GLYCOSIDASE; IMINOSUGAR; MANNITOL; PYRROLIDINE DERIVATIVE;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; DRUG SYNTHESIS; HYDROXYLATION; ISOMER; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REDUCTION; STEREOCHEMISTRY; X RAY CRYSTALLOGRAPHY; CHEMICAL STRUCTURE; CHEMISTRY; DRUG ANTAGONISM; ISOMERISM; SYNTHESIS;

ALKALOIDS; ENZYME INHIBITORS; GLYCOSIDE HYDROLASES; IMINO FURANOSES; ISOMERISM; MANNITOL; MOLECULAR STRUCTURE; PYRROLES; PYRROLIDINES;

EID: 0037572030     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol027504h     Document Type: Article

References (17)

1. See: (a) White, J. D.; Hrnciar, P. J. Org. Chem. 2000, 65, 9129. (b) Asano, N.; Kuroi, H.; Ikeda, K.; Kizu, H.; Kameda, Y.; Kato, A.; Adachi, I.; Watson, A. A.; Nash, R. J.; Fleet, G. W. J. Tetrahedron: Asymmetry 2000, 11, 1.
2. See: (a) White, J. D.; Hrnciar, P. J. Org. Chem. 2000, 65, 9129. (b) Asano, N.; Kuroi, H.; Ikeda, K.; Kizu, H.; Kameda, Y.; Kato, A.; Adachi, I.; Watson, A. A.; Nash, R. J.; Fleet, G. W. J. Tetrahedron: Asymmetry 2000, 11, 1.
3. (a) Donohoe, T. J.; Guyo, P. M. J. Org. Chem. 1996, 61, 7664.
4. (b) Donohoe, T. J.; Guyo, P. M.; Beddoes, R. L.; Helliwell, M. J. Chem. Soc., Perkin Trans. 1 1998, 667.
5. Donohoe, T. J.; Harji, R. R.; Cousins, R. P. C. Tetrahedron Lett. 2000, 41, 1327.
6. Evans, S. V.; Fellows, L. E.; Shing, T. K. M.; Fleet, G. W. J. Phytochemistry 1985, 24, 1953.
7. Hasan, I.; Marinelli, E. R.; Lin, L.-C. C.; Fowler, F. W.; Levy, A. B. J. Org. Chem. 1981, 46, 157.
8. (a) Donohoe, T. J.; Harji, R. R.; Cousins, R. P. C. Tetrahedron Lett. 2000, 41, 1331.
9. (b) Donohoe, T. J.; House, D. J. Org. Chem. 2002, 67, 5015.
10. 3 While reductive alkylation proceeds to give the trans isomers exclusively, protonation in ammonia had been reported to give a (7:3) mixture of cis and trans isomers. This ratio is our error, and further study confirms that reduction (followed by protonation) in ammonia definitely proceeds to give the trans isomer as the major compound (6:1).
11. Schultz, A. G.; Macielag, M.; Sundararaman, P.; Taveras, A. G.; Welch, M. J. Am. Chem. Soc. 1988, 110, 7828.
12. See: Seebach, D. Angew. Chem., Int. Ed. Engl. 1988, 27, 1624. This is reminiscent of the Grotthus mechanism for proton transfer in water; see: Pilling, M. J.; Seakins, P. W. Reaction Kinetics; Oxford University Press: New York, 1995.
13. See: Seebach, D. Angew. Chem., Int. Ed. Engl. 1988, 27, 1624. This is reminiscent of the Grotthus mechanism for proton transfer in water; see: Pilling, M. J.; Seakins, P. W. Reaction Kinetics; Oxford University Press: New York, 1995.
14. 3, APT) δ 63.0 (+), 69.3 (-), 72.7 (+), 73.3 (-), 127.7 (+), 127.8 (+), 128.5 (+), 137.6 (-).
15. 3) δ 64.3, 72.1, 74.0, 81.0, 128.3, 128.4, 129.0, 137.9.
16. 1H NMR spectrum of (+)-DMDP, see: Fechter, M. H.; Gradnig, G.; Berger, A.; Mirtl, C.; Schmid, W.; Stütz, A. E. Carbohydr. Res. 1998, 309, 367. For general references to the isolation and previous syntheses of DMDP, see: Izquierdo, I.; Plaza, M. T.; Franco, F. Tetrahedron: Asymmetry 2002, 13, 1503.
17. 1H NMR spectrum of (+)-DMDP, see: Fechter, M. H.; Gradnig, G.; Berger, A.; Mirtl, C.; Schmid, W.; Stütz, A. E. Carbohydr. Res. 1998, 309, 367. For general references to the isolation and previous syntheses of DMDP, see: Izquierdo, I.; Plaza, M. T.; Franco, F. Tetrahedron: Asymmetry 2002, 13, 1503.