Asymmetric Total Synthesis of (+)-Mycoepoxydiene: Application of One-Pot Ring-Opening/Cross/Ring-Closing Metathesis
摘要:
The asymmetric total syntheses of (+)-mycoepoxydiene and (–)-1893A have been completed. The present synthetic strategy features the use of one-pot ring-opening/cross metathesis (ROM/CM) followed by a ring-closing metathesis (RCM) reaction, allowing the concise construction of the 9-oxabicyclo[4.2.1]nona-2,4-diene framework from a 7-oxabicyclo[2.2.1]hept-2-ene derivative and 1,3-butadiene. The sequential metathesis product was converted into (+)-mycoepoxydiene through the oxidative rearrangement of a furfuryl alcohol to a pyranone, thereby establishing its absolute stereochemistry. From the common intermediate, a structurally related natural product (–)-1893A was also synthesized via the vinylogous aldol reaction.
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关键词:
asymmetric total synthesis ring-opening/cross metathesis ring-closing metathesis 9-oxabicyclo[4.2.1]nona-2,4-diene
DOI:
10.14895/hannou.30.0.12.0
年份:
2004
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