Development of domino cyclization reaction for one-pot synthesis of pyrroloindolizines and its application to total syntheses of related alkaloids
| 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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Report
(3 results)
Research Products
(21 results)
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[Presentation]2013
Author(s)
山本のぞみ、杉本健士、湊大志郎、松谷裕三
Organizer
平成25年度有機合成化学北陸セミナー
Place of Presentation
石川県金沢市
Related Report
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[Presentation]2013
Author(s)
山本のぞみ、杉本健士、湊大志郎、松谷裕三
Organizer
日本薬学会第133年会
Place of Presentation
神奈川県横浜市
Related Report
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[Presentation]2012
Author(s)
杉本健士、保志場友哉、山本のぞみ、松谷裕三
Organizer
日本薬学会北陸支部第124回例会
Place of Presentation
富山県富山市
Year and Date
2012-11-18
Related Report
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[Presentation]2012
Author(s)
保志場友哉、杉本健士、松谷裕三
Organizer
第38回反応と合成の進歩シンポジウム
Place of Presentation
東京都江戸川区
Related Report
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[Presentation]2012
Author(s)
保志場友哉、杉本健士、松谷裕三
Organizer
平成24年度有機合成化学北陸セミナー
Place of Presentation
富山県富山市
Related Report
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