Functionalized templates for the convergent assembly of polyethers: Synthesis of the HIJK rings of gymnocin A

Angewandte Chemie - International Edition

Volumn 48, Issue 24, 2009, Pages 4430-4432

  Van Dyke, Aaron R ^a   Jamison, Timothy F ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

Cascade reactions; Metathesis; Natural products; Polyethers; Template synthesis

Indexed keywords

CASCADE REACTIONS; EXTENSION LADDERS; FRAGMENT COUPLING; FUNCTIONALIZED; GYMNOCIN-A; METATHESIS; NATURAL PRODUCTS; TEMPLATE SYNTHESIS;

ETHERS; POLYETHERS;

SYNTHESIS (CHEMICAL);

ETHER DERIVATIVE; GYMNOCIN A;

CHEMISTRY; CYCLIZATION; SYNTHESIS;

CYCLIZATION; ETHERS; ETHERS, CYCLIC;

EID: 70349777757     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200900924     Document Type: Article

References (18)

1. For an excellent and recent review of the ladder polyether natural products, see: a) K. C. Nicolaou, M. O. Frederick, R. J. Aversa, Angew. Chem. 2008, 120, 7292-1335;
2. Angew. Chem. Int. Ed. 2008, 47, 7182-7225.
3. I. Vilotijevic, T. F. Jamison, Science 2007, 317, 1189-1192.
4. K. C. Nicolaou, D. A. Nugiel, E. Couladouros, C. K. Hwang, Tetrahedron 1990, 46, 4517-4552.
5. K. C. Nicolaou, M. E. Duggan, T. Ladduwahetty, Tetrahedron Lett. 1984, 25, 2069-2072.
6. Silica gel has been used for endo-selective epoxysilane opening but not, to our knowledge, for electronically unbiased epoxides such as 5. We confirmed that the allyl substituent was not electronically biasing the epoxide as studies with fully saturated analogues gave comparable results, see: G. Adiwidjaja, H. Flörke, A. Kirschning, E. Schaumann, Tetrahedron Lett. 1995, 56, 8771-8774.
7. 2.
8. Given the mildly acidic nature of silica gel, we did not predict it would be an effective promoter for an epoxide-opening cascade reaction. Indeed, in studies of templates bearing two epoxide groups, silica-based promoters led to the formation of undesired oxetane and tetrahydrofuran rings.
9. G. Koch, O. Loiseleur, K.-H. Altmann, Synlett 2004, 693-697.
10. H. Fuwa, M. Sasaki, K. Tachibana, Tetrahedron 2001, 57, 3019- 3033.
11. G. Sabitha, K. Sudhakar, N. M. Reddy, M. Rajkumar, J. S. Yadav, Tetrahedron Lett. 2005, 46, 6567-6570.
12. S. J. Connon, S. Blechert, Angew. Chem. 2003, 115, 1944-1968;
13. Angew. Chem. Int. Ed. 2003, 42, 1900-1923.
14. a) H. E. Blackwell, D. J. O'Leary, A. K. Chatterjee, R. A. Washenfelder, D. A. Bussmann, R. H. Grubbs, J. Am. Chem. Soc. 2000, 122, 58-71;
15. b) D. J. O'Leary, H. E. Blackwell, R. A. Washenfelder, R. H. Grubbs, Tetrahedron Lett. 1998, 39, 7427-7430.
16. Although cross-metathesis afforded ample quantities of 16 to evaluate ring K as a template in epoxide-opening cascade reactions, we are investigating other more general strategies for the construction of similar "skipped" polyepoxides.
17. Y. Tu, Z-X. Wang, Y. Shi, J. Am. Chem. Soc. 1996, 118, 9806-9807.
18. J. A. Byers, T. F. Jamison, J. Am. Chem. Soc. 2009, 131, Article ASAP, DOI: 10.1021/ja9004909.