| Project/Area Number |
24790007
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| Research Category |
Grant-in-Aid for Young Scientists (B)
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| Allocation Type | Multi-year Fund |
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| Research Field |
Chemical pharmacy
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| Research Institution | University of Toyama |
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Principal Investigator |
SUGIMOTO Kenji 富山大学, 大学院医学薬学研究部(薬学), 准教授 (60400264)
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| Project Period (FY) |
2012-04-01 – 2014-03-31
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| Project Status |
Completed (Fiscal Year 2013)
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| Budget Amount *help |
¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000)
Fiscal Year 2013: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2012: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
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| Keywords | イミノエステル / アゾメチンイリド / [3+2]付加環化反応 / エナミン環化 / 金触媒 / ピロロインドリジン / ピロロピロリジン |
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| Research Abstract |
We could find a gold-catalyzed domino reaction including an activation of triple bond, 6-exo-dig cyclization from imine nitrogen, generation of azomethine ylide, and enamine cyclization.
Alkynyl iminoesters could be transformed into indolizines as a sole diastereomer. The X-ray crystallographic analysis on phenylmenthyl ester derivative revealed the configuration of the products and the mechanism on the observed stereoselectivities. However, the enamine cyclization, the final step for pyrroloindolizine formation, could not proceed at all because of the isomerization of the exo-enamine into the inappropriate endo-enamine via a conjugation with aromatic ring. After the investigations on the enamine cyclization step with intermolecular approach for a preclusion of undesired isomerization, we finally realized that trifluoroethyl ester worked best as an electrophile to give hydroxypyrroles in one-pot process. Based on these findings, synthetic studies on myrmicarins are now in progress.
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