Rapid Two-Directional Synthesis of the F-J Fragment of the Gambieric Acids by Iterative Double Ring-Closing Metathesis

• Published in: Angewandte Chemie (International ed.) Vol. 44; no. 38; pp. 6157 - 6162
• Main Authors: Clark, J. Stephen, Kimber, Marc C., Robertson, Jerod, McErlean, Christopher S. P., Wilson, Claire
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 26.09.2005; WILEY‐VCH Verlag; Wiley
• Subjects: Animals; Antifungal Agents - chemical synthesis; Antifungal Agents - chemistry; Chemistry; Chemistry, Multidisciplinary; Ciguatoxins - chemical synthesis; Ciguatoxins - chemistry; cyclization; Dinoflagellida - chemistry; Ethers, Cyclic - chemical synthesis; Ethers, Cyclic - chemistry; metathesis; Molecular Structure; natural products; Physical Sciences; polyethers; Science & Technology; POLYETHER SYNTHESIS; SUB-UNITS; BIOLOGICAL-ACTIVITIES; CIGUATOXIN CTX3C; cyclization; POTENT ANTIFUNGAL SUBSTANCES; POLYCYCLIC ETHERS; DINOFLAGELLATE GAMBIERDISCUS-TOXICUS; BREVETOXIN-B; natural products; polyethers; metathesis; PRACTICAL TOTAL-SYNTHESIS; CHAIN SYNTHESIS
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.200501925

D‐glucal is the starting point for the efficient synthesis of the F–J fragment of the gambieric acids (see scheme). The H‐ring diol was subjected to double two‐directional alkynyl ether formation, carbocupration ring‐closing metathesis, and hydroboration. The tricyclic G–I diol was then converted into the F–J fragment by a sequence that involves another double two‐directional ring‐closing metathesis reaction.