A remarkable pyranose to furanose isomerization mediated by an 'anomeric' silyloxy function

Tetrahedron Letters

Volumn 40, Issue 17, 1999, Pages 3313-3316

  Bhattacharya, Samit K ^a   Chen, Xiao Tao ^a   Gutteridge, Clare E ^a   Danishefsky, Samuel J ^a,b  

^a Och Spine at New York Presbyterian Hospitals   (United States)

^b MEMORIAL SLOAN KETTERING CANCER CENTER   (United States)

Author keywords

Antitumor compounds; Eleutherobin; Isomerization; Rearrangements

Indexed keywords

ELEUTHEROBIN; FURAN DERIVATIVE; FURANOSE; NATURAL PRODUCT; PYRAN DERIVATIVE; PYRANOSE; UNCLASSIFIED DRUG;

ANTINEOPLASTIC ACTIVITY; ARTICLE; CONFORMATIONAL TRANSITION; CRYSTALLOGRAPHY; DRUG SYNTHESIS; ISOMERISM; METHYLATION; NUCLEAR OVERHAUSER EFFECT; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 0033597271     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)00499-2     Document Type: Article

References (8)

1. [1] Chen, X. -T.; Gutteridge, C. E.; Bhattacharya, S. K.; Zhou, B.; Pettus, T. R. R.; Hascall, T.; Danishefsky, S. J. Angew. Chem. Int. Ed. Engl. 1998, 37, 185.
2. [2] Chen, X. -T.; Zhou, B.; Bhattacharya, S. K.; Gutteridge, C. E.; Pettus, T. R. R.; Danishefsky, S. J. Angew. Chem. Int. Ed. Engl. 1998, 37, 789.
3. [3] a) Lindel, T.; Fenical, W. H.; Jensen, P. R.; Long, B. H.; Casazza, A. M.; Carboni, J.; Fairchild, C. R. J. Am. Chem. Soc. 1997, 119, 8744;
4. b) Long, B. H.; Fairchild, C. R.; Wasserman, A. J.; Carboni, J.; Casazza, A. M.; Fenical, W. H. Cancer Research 1998, 58, 1111.
5. [4] Almost 10 equivalents of the organometallic reagent were necessitated to drive the reaction to completion. As long as the temperature remained at ~-78°C and the reaction was quenched at the same low temperature, only the desired product was obtained.
6. [5] For a discussion on out-out and in-out arrangements in bridged compounds see: Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic compounds, Wiley, New York, 1994, pp. 791-793.
7. rel (kcal/mol) = 0 (out-out), 12.35 (H in-OTMS out), 14.33 (H out-OTMS in).
8. [7] Although good diffraction patterns were obtained from the crystals, the structure could not be refined beyond an R factor of 0.15.