Synthetic Strategies for the Total Synthesis of Pyranonaphthoquinone Type Natural Products
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19K21125
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| Project/Area Number (Other) |
18H05972 (2018)
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| Research Category |
Grant-in-Aid for Research Activity Start-up
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| Allocation Type | Multi-year Fund (2019)
Single-year Grants (2018) |
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| Review Section |
0501:Physical chemistry, functional solid state chemistry, organic chemistry, polymers, organic materials, biomolecular chemistry, and related fields
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
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| Project Period (FY) |
2018-08-24 – 2020-03-31
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| Project Status |
Completed (Fiscal Year 2019)
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| Budget Amount *help |
¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2019: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000)
Fiscal Year 2018: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
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| Keywords | naphthocyclinones / natural products / Claisen rearrangement / total synthesis / pyranonapthoquinons / aromatic polyketides / pyranonaphthoquinone / polyketide |
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| Outline of Research at the Start |
The synthesis of a dihydropyrone annulated naphthalene - a key intermediate to various members of the pyranonaphthoquinone family - as well as its the efficient modification and the investigation of a dearomative Claisen rearrangement will be conducted.
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| Outline of Final Research Achievements |
The efficient synthesis of two building blocks has been achieved. For the Synthesis of the aromatic building block, a three-step protocoll has been developed and partly published. This includes a highly regioselective benzocyclobutenol formation followed by bond-selective cyclobuten ring opening to access o-methylbenzaldehydes. The synthesis of a Claisen-precursor was optimized and allowed synthesis of the latter in 12 steps. The dearomative Claisen rearrangement (CR) was first investigated with a deuterium-labelled model compound. The results strongly suggest a reaction pathway following the classical CR via a 3,3-sigmatropic shift. Optimization of the reaction conditions for the CR on the real system was developed and comprises a two-step protocol. The developed synthesis allows for the construction of a synthetic intermediate for ruthmycin bearing the full carbon skeleton with an angular stereogenic center with perfect stereocontrol.
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| Academic Significance and Societal Importance of the Research Achievements |
The study of interest to the synthetic community investigation natural product synthesis of complex molecules.
The discovery of the new Claisen Rearrangement and its investigation will stimulate further research.
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Report
(3 results)
Research Products
(4 results)
