Total Synthesis of (+)-Psymberin (Irciniastatin A): Catalytic Reagent Control as the Strategic Cornerstone

An effective total synthesis of the marine sponge cytotoxin (+)-psymberin [irciniastatin A (1)] has been achieved. Highlights of the strategy include a Diels−Alder reaction between a bis-siloxy diene and an allene to construct the aromatic ring, a boron-mediated aldol reaction to elaborate the C(15−...

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Bibliographic Details
Published inOrganic letters Vol. 10; no. 24; pp. 5625 - 5628
Main Authors Smith, Amos B, Jurica, Jon A, Walsh, Shawn P
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 18.12.2008
Amer Chemical Soc
Subjects
Animals
Catalysis
Chemistry
Chemistry, Organic
Coumarins - chemical synthesis
Coumarins - chemistry
Cytotoxins - chemical synthesis
Cytotoxins - chemistry
Physical Sciences
Porifera - chemistry
Pyrones
Science & Technology
OXIDATION
KETONES
DIASTEREOSELECTIVE ALDOL REACTIONS
CONFIGURATION
ALDEHYDES
PSYMBERIN
ETHYL
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Summary:An effective total synthesis of the marine sponge cytotoxin (+)-psymberin [irciniastatin A (1)] has been achieved. Highlights of the strategy include a Diels−Alder reaction between a bis-siloxy diene and an allene to construct the aromatic ring, a boron-mediated aldol reaction to elaborate the C(15−17) all syn stereotriad, catalytic reagent control to set the C(8, 9, 11 and 13) stereogenic centers of the tetrahydropyran core, and a late-stage Curtius rearrangement to install the sensitive N,O-aminal moiety. The synthesis proceeds with a longest linear sequence of 21 steps from commercially available 2,2-dimethyl-1,3-propanediol.
Bibliography:NIH RePORTER
ISSN:1523-7060
1523-7052
DOI:10.1021/ol802466t