Document Detail

SmI2-induced cyclizations and their applications in natural product synthesis.
MedLine Citation:
PMID:  20503205     Owner:  NLM     Status:  MEDLINE    
Since the isolation of brevetoxin-B, a red tide toxin, many bioactive marine natural products featuring synthetically challenging trans-fused polycyclic ether ring systems have been reported. We have developed SmI(2)-induced cyclization of beta-alkoxyacrylate with aldehyde, affording 2,6-syn-2,3-trans-tetrahydropyran (THP) or 2,7-syn-2,3-trans-oxepane with complete stereoselection, as a key reaction of efficient iterative and bi-directional strategies for the construction of these polycyclic ethers. This reaction is also applicable to the synthesis of 3-, 5-, and 6-methyl-THPs and 3,5-dimethyl-THP. The synthesis of 2-methyl- and 2,6-dimethyl-THPs was accomplished by means of a unique methyl insertion. Recently, the SmI(2)-induced cyclization was extended to similar reactions using beta-alkoxyvinyl sulfone and sulfoxide. Reaction of (E)- and (Z)-beta-alkoxyvinyl sulfone-aldehyde afforded 2,6-syn-2,3-trans- and 2,6-syn-2,3-cis- THPs, respectively. Reaction of (E)-beta-alkoxyvinyl (R)- and (S)-sulfoxides gave 2,6-anti-2,3-cis- and 2,6-syn-2,3-trans-THPs, respectively. Reaction of (Z)-beta-alkoxyvinyl (R)-sulfoxides gave 2,6-syn-2,3-cis-THP and an olefinic product, while that of (Z)-beta-alkoxyvinyl (S)-sulfoxide afforded a mixture of many products. These SmI(2)-induced cyclizations have been applied to the total syntheses of various natural products, including brevetoxin-B, mucocin, pyranicin, and pyragonicin. Synthetic studies on gambierol and maitotoxin are also introduced.
Tadashi Nakata
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't; Review    
Journal Detail:
Title:  Chemical record (New York, N.Y.)     Volume:  10     ISSN:  1528-0691     ISO Abbreviation:  Chem Rec     Publication Date:  2010 Jun 
Date Detail:
Created Date:  2010-06-21     Completed Date:  2010-09-16     Revised Date:  2010-10-20    
Medline Journal Info:
Nlm Unique ID:  101085550     Medline TA:  Chem Rec     Country:  United States    
Other Details:
Languages:  eng     Pagination:  159-72     Citation Subset:  IM    
Copyright Information:
2010 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.
Department of Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo162-8601, Japan.
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MeSH Terms
Biological Products / chemical synthesis*,  chemistry
Ciguatoxins / chemical synthesis,  chemistry
Ethers / chemical synthesis,  chemistry
Heterocyclic Compounds with 4 or More Rings / chemical synthesis,  chemistry
Iodides / chemistry*
Lactones / chemical synthesis,  chemistry
Marine Toxins / chemical synthesis,  chemistry
Oxocins / chemical synthesis,  chemistry
Polymers / chemical synthesis,  chemistry
Pyrans / chemical synthesis,  chemistry
Samarium / chemistry*
Reg. No./Substance:
0/Biological Products; 0/Ethers; 0/Heterocyclic Compounds with 4 or More Rings; 0/Iodides; 0/Lactones; 0/Marine Toxins; 0/Oxocins; 0/Polymers; 0/Pyrans; 0/brevenal (polyether); 0/gambierol; 0/mucocin; 0/samarium diiodide; 11050-21-8/Ciguatoxins; 122271-91-4/hemibrevetoxin B; 59392-53-9/maitotoxin; 7440-19-9/Samarium; 79580-28-2/brevetoxin B

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