Total synthesis of (--)-amphidinolide P through cross ene-yne and intramolecular olefin metathesis, relay ring closing olefin/cross ene-yne metathesis
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Synthesis of (-)-amphidinolide P Very few examples of ene-yne and enyne metatheses are currently known and being used in total synthesis. Even within the scope of this project, several of the enyne metatheses were unsuccessful, and the synthesis needed to be redesigned. More investigation of enyne metathesis is necessary in order to select the ideal substrates, catalysts, and reaction conditions, and to avoid unsuccessful enyne metathesis. A broad optimization of ene-yne metathesis was performed. The presence of unprotected alcohol increased the reaction rate so that the reaction could be completed at low temperature conditions and side reactions could be suppressed. The intramolecular enyne metathesis was investigated by varying the starting materials but no successful conditions were found. Instead, the alkyne was converted to butadiene and a successful olefin macro cyclization was completed. The use of ene-yne and enyne metatheses allowed the synthesis of (-)-amphidinolide P. The structure was proven by spectroscopic methods. Relay ring closing olefin/ cross ene-yne metathesis Usually geminally disubstituted alkenes are not used for cross ene-yne metathesis due to poor catalyst initiation on alkenes. A relay ring closing olefin/ cross ene-yne metathesis was developed in Professor Diver's research group. In this thesis, cycloheptylidene transfer is demonstrated. A possible application of the relay strategy for the synthesis of amphidinolide P is also discussed.
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