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New Synthetic Strategy for Carbonyl Compounds Based on Palladium Enolate Umpolung

Research Project

Project/Area Number 15K05501
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionOsaka University

Principal Investigator

Takenaka Kazuhiro  大阪大学, 産業科学研究所, 特任准教授 (20423113)

Research Collaborator MOHANTA Suman C.  
SAWADA Kazuya  
NOMOTO Yuya  
Project Period (FY) 2015-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2017: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2016: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2015: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywordsパラジウム触媒 / エノラート / 極性転換 / カルボニル化合物 / パラジウム
Outline of Final Research Achievements

Palladium enolates are known not to exhibit any reactivity toward a nucleophile but to react with an electrophile. Nucleophilic interception of the palladium enolate is therefore promising to be a powerful synthetic method of functionalized carbonyl compounds. Through the present study, new catalytic reactions based on palladium enolate umpolung have been successfully developed, which provide an efficient route to valuable bicyclic carbonyl compounds from readily available substrates. These processes involve ring-closing carbon-carbon bond formation and subsequent nucleophilic attack at the resulting palladium enolate intermediate.

Academic Significance and Societal Importance of the Research Achievements

アミノ酸を代表とするカルボニル化合物は、医薬品や農薬など様々な製品に利用されている重要な化合物群である。本研究では、今までは進行しないと思われてきたプロセスが条件次第では達成できることを見出した。この成果を基にすれば、現代社会を支えるカルボニル化合物製品の開発において、反応剤の選択肢を大幅に広げるだけでなく新しい合成戦略の提案にも繋げられ、製造コストの削減や製造時の安全性向上といった改善が期待できる。

Report

(5 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Research-status Report
  • 2016 Research-status Report
  • 2015 Research-status Report
  • Research Products

    (52 results)

All 2019 2018 2017 2016 2015

All Journal Article (6 results) (of which Peer Reviewed: 5 results,  Acknowledgement Compliant: 3 results) Presentation (46 results) (of which Int'l Joint Research: 14 results)

  • [Journal Article] Enantioselective synthesis of spiro (isoxazole-isoxazoline) hybrid ligands2018

    • Author(s)
      B. M. Chaki, K. Wakita, S. Takizawa, K. Takenaka, H. Sasai
    • Journal Title

      Heterocycles

      Volume: - Issue: 1 Pages: 493-505

    • DOI

      10.3987/com-18-s(t)41

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Aza-Wacker-Type Cyclization Promoted by Pd-SPRIX Catalyst2018

    • Author(s)
      Sen, A.; Takenaka, K.; Sasai, H.
    • Journal Title

      Org. Lett.

      Volume: 20 Issue: 21 Pages: 6827-6831

    • DOI

      10.1021/acs.orglett.8b02946

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Pd-catalyzed enantioselective intramolecular α-arylation of α-substituted cyclic ketones: Facile synthesis of functionalized chiral spirobicycles2015

    • Author(s)
      L. Fan, S. Takizawa, Y. Takeuchi, K. Takenaka, H. Sasai
    • Journal Title

      Org. Biomol. Chem.

      Volume: 13 Issue: 17 Pages: 4837-4840

    • DOI

      10.1039/c5ob00382b

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Structural Features and Asymmetric Environment of i-Pr-SPRIX Ligand2015

    • Author(s)
      Takenaka, K.; Lin, X.; Takizawa, S.; Sasai, H.
    • Journal Title

      Chirality

      Volume: 27 Issue: 8 Pages: 532-537

    • DOI

      10.1002/chir.22467

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Palladium-Catalyzed Direct C-H Arylation of Isoxazoles at the 5-Position2015

    • Author(s)
      Shigenobu, M.; Takenaka, K.; Sasai, H.
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 54 Issue: 33 Pages: 9572-9576

    • DOI

      10.1002/anie.201504552

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] パラジウム(II)錯体の反応性制御 新規エナンチオ選択的パラジウム触媒反応の開発2015

    • Author(s)
      竹中和浩
    • Journal Title

      化学と工業

      Volume: 68 Pages: 1123-1124

    • Related Report
      2015 Research-status Report
  • [Presentation] Facile Synthesis of Allylamines via Intermolecular Aza-Wacker-Type Reaction Promoted by a Pd-SPRIX Catalyst2019

    • Author(s)
      Abhijit Sen、竹中和浩、笹井宏明
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Effect of Phosphine Ligands on Pd-catalyzed Cyclative Hydroamination2019

    • Author(s)
      草場未来、竹中和浩、笹井宏明
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Development of New Chiral Ligands Based on a Tetraphenylene Backbone2019

    • Author(s)
      片岡航佑、竹中和浩、笹井宏明
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Enantioselective Synthesis of Bicyclic Pyrrolidine Derivatives via One-Pot Sequential Organo and Palladium Catalysis2018

    • Author(s)
      Chaki, B. M.; Zhu, L.; Takenaka, K.; Bai, J.; Takizawa, S.; Sasai, H.
    • Organizer
      The 14th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-14)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Catalytic Cyclative Hydroamination Based on Palladium Enolate Umpolung2018

    • Author(s)
      Nomoto, Y.; Kusaba, M.; Takenaka, K.; Sasai, H.
    • Organizer
      International Research Training Group “SELECTIVITY IN CHEMO- AND BIOCATALYSIS” FINAL AACHEM-OSAKA SYMPOSIUM
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 有機分子-パラジウム連続触媒反応を活用する二環式ピロリジン誘導体のエナンチオ選択的ワンポット合成2018

    • Author(s)
      竹中和浩、Bijan Mohon Chaki、Jianfei Bai、滝澤忍、笹井宏明
    • Organizer
      Symposium on Molecular Chirality 2018
    • Related Report
      2018 Annual Research Report
  • [Presentation] 連続触媒プロセスによる二環式ピロリジン誘導体のエナンチオ選択的ワンポット合成2018

    • Author(s)
      竹中和浩、Bijan Mohon Chaki、Jianfei Bai、滝澤忍、笹井宏明
    • Organizer
      日本プロセス化学会2018サマーシンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] エナンチオ選択的パラジウム2価ー4価触媒反応を基盤とする二環式ピロリジン誘導体のワンポット合成2018

    • Author(s)
      竹中和浩、Bijan Mohon Chaki、Linpeng ZHU、Jianfei Bai、滝澤忍、笹井宏明
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Pd-SPRIX触媒を用いるaza-Wacker型反応の開発2018

    • Author(s)
      Abhijit Sen、竹中和浩、笹井宏明
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Enantioselective Synthesis of Bicyclic Pyrrolidine Derivatives via One-pot Sequential Organo- and Pd-Catalysis2018

    • Author(s)
      Chaki, B. M.; Bai, J.; Takenaka, K.; Takizawa, S.; Sasai, H.
    • Organizer
      21st SANKEN International Symposium
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Enantioselective Synthesis of Bicyclic Pyrrolidine Derivatives via One-Pot Organo and Palladium Catalysis2018

    • Author(s)
      Chaki, B. M.; Bai, J.; Takenaka, K.; Takizawa, S.; Sasai, H.
    • Organizer
      Biotechnology and Chemistry for Green Growth
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Development of New Spiro-type Chiral Ligands Bearing a Functional Side Arm2018

    • Author(s)
      新居田恭章、竹中和浩、笹井宏明
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] Palladium Enolate Umpolung: Approach to α-Aminocarbonyl Compounds2018

    • Author(s)
      野本裕也、竹中和浩、笹井宏明
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] Enantioselective Synthesis of Nitrogen Heterocycles via aza-Wacker-type Reaction Catalyzed by Pd-SPRIX Complex2018

    • Author(s)
      Abhijit Sen、竹中和浩、笹井宏明
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] Enantioselective Synthesis of Bicyclic Pyrrolidine Derivatives via One-Pot Organo and Palladium Catalysis Relay2018

    • Author(s)
      Bijan M. Chaki、Jianfei Bai、竹中和浩、滝澤忍、笹井宏明
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] Enantioselective aza-Wacker Reaction Promoted by Pd-SPRIX2017

    • Author(s)
      Abhijit Sen、竹中和浩、笹井宏明
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應大学(神奈川)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] Pd(II)-SPRIX Catalyzed Enantioselective Annulation of Alkenylindoles: Allyl Group Assisted Construction of Quaternary Carbon Center2017

    • Author(s)
      Mohamed A. Abozeid、滝澤忍、竹中和浩、笹井宏明
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應大学(神奈川)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] Development of Novel Spiro-type Chiral Ligands Bearing Pyrazole Donors2017

    • Author(s)
      重信匡志、竹中和浩、笹井宏明
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應大学(神奈川)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] Enantioselective Synthesis of Bicyclic Pyrrolidine Derivatives via Sequential Organo- and Pd-Catalysis2017

    • Author(s)
      Bijan M. Chaki、Jianfei Bai、竹中和浩、滝澤忍、笹井宏明
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應大学(神奈川)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] α-Functionalization of Carbonyl Compounds Based on Palladium Enolate Umpolung2017

    • Author(s)
      野本裕也、澤田和弥、竹中和浩、笹井宏明
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應大学(神奈川)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] Development of Novel Spiro-Type Chiral Ligands Bearing Pyrazole Donors2017

    • Author(s)
      Shigenobu, M.; Takenaka, K.; Sasai, H.
    • Organizer
      Biotechnology and Chemistry for Green Growth
    • Place of Presentation
      Awaji Island, Japan
    • Year and Date
      2017-03-06
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Enantioselective Aza-Wacker Reaction Promoted by Pd-SPRIX Catalyst2017

    • Author(s)
      Sen, A.; Takenaka, K.; Sasai, H.
    • Organizer
      Biotechnology and Chemistry for Green Growth
    • Place of Presentation
      Awaji Island, Japan
    • Year and Date
      2017-03-06
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Enantioselective Aza-Wacker-Type Reaction Promoted by Pd-SPRIX Catalyst2017

    • Author(s)
      Sen, A.; Takenaka, K.; Sasai, H.
    • Organizer
      Chirality 2017
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Enantioselective Aza-Wacker-Type Reaction Promoted by Pd-SPRIX Catalyst2017

    • Author(s)
      Sen, A.; Takenaka, K.; Sasai, H.
    • Organizer
      The 11th International Symposium on Integrated Synthesis (ISONIS-11), The 3rd International Symposium on Middle Molecular Strategy (ISMMS-3)
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] パラジウムエノラートの極性転換を利用する多官能性カルボニル化合物の効率合成2017

    • Author(s)
      野本裕也、竹中和浩、澤田和弥、Suman C. Mohanta、笹井宏明
    • Organizer
      第111回有機合成シンポジウム
    • Related Report
      2017 Research-status Report
  • [Presentation] Enantioselective Aza-Wacker-Type Reaction Promoted by Pd-SPRIX Catalyst2017

    • Author(s)
      Abhijit Sen、竹中和浩、笹井宏明
    • Organizer
      日本プロセス化学会2017サマーシンポジウム
    • Related Report
      2017 Research-status Report
  • [Presentation] α-アミノカルボニル化合物を与えるパラジウムエノラートの極性転換型求核的アミノ化反応の開発2017

    • Author(s)
      野本裕也、竹中和浩、笹井宏明
    • Organizer
      日本プロセス化学会2017サマーシンポジウム
    • Related Report
      2017 Research-status Report
  • [Presentation] Pd-SPRIX触媒を用いるエナンチオ選択的分子内aza-Wacker型環化反応2017

    • Author(s)
      Sen Abhijit、片岡航佑、竹中和浩、笹井宏明
    • Organizer
      第37回有機合成若手セミナー
    • Related Report
      2017 Research-status Report
  • [Presentation] Development of Catalytic Synthetic Method for α-Amino Carbonyl Compounds Based on Palladium Enolate Umpolung2017

    • Author(s)
      竹中和浩、野本裕也、笹井宏明
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] Enantioselective aza-Wacker-Type Reaction Promoted by Pd-SPRIX Catalyst2017

    • Author(s)
      Sen Abhijit、竹中和浩、笹井宏明
    • Organizer
      第34回有機合成化学セミナー
    • Related Report
      2017 Research-status Report
  • [Presentation] Recent Progress on Pd-SPRIX Catalyzed Enantioselective Reactions2016

    • Author(s)
      Chaki, B. M.; Mohanta, S. C.; Abozeid, M. A.; Takenaka, K.; Takizawa, S.; Sasai, H.
    • Organizer
      The 10th International Symposium on Integrated Synthesis
    • Place of Presentation
      Awaji Island, Japan
    • Year and Date
      2016-11-18
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] パラジウムエノラートの極性転換を活用するカルボニル化合物の触媒的環化官能基化反応2016

    • Author(s)
      竹中和浩、澤田和弥、Suman C. Mohanta、笹井宏明
    • Organizer
      第46回複素環化学討論会
    • Place of Presentation
      金沢歌劇座(石川)
    • Year and Date
      2016-09-26
    • Related Report
      2016 Research-status Report
  • [Presentation] Palladium Enolate Umpolung: Catalytic Cyclative Hydroacyloxylation of Alkynyl Cyclohexadienones2016

    • Author(s)
      竹中和浩、澤田和弥、Suman C. Mohanta、笹井宏明
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      早稲田大学西早稲田キャンパス(東京)
    • Year and Date
      2016-09-14
    • Related Report
      2016 Research-status Report
  • [Presentation] パラジウムエノラートの極性転換を基軸とする多官能性カルボニル化合物の効率的合成2016

    • Author(s)
      竹中和浩、澤田和弥、Suman C. Mohanta、笹井宏明
    • Organizer
      日本プロセス化学会2016サマーシンポジウム
    • Place of Presentation
      名古屋国際会議場(愛知)
    • Year and Date
      2016-07-28
    • Related Report
      2016 Research-status Report
  • [Presentation] Palladium Enolate Umpolung: Catalytic Cyclative Difunctionalization of Alkynyl Cyclohexadienones Using SPRIX Ligand2016

    • Author(s)
      Takenaka, K.; Mohanta, S. C.; Sasai, H.
    • Organizer
      Molecular Chirality Asia 2016
    • Place of Presentation
      Osaka, Japan
    • Year and Date
      2016-04-20
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Palladium Enolate Umpolung: Cyclative Haloacetoxylation of Alkynyl Cyclohexadienones2016

    • Author(s)
      竹中和浩、Suman C. Mohanta、笹井宏明
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学京田辺キャンパス
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] Palladium Enolate Umpolung: Cyclative Hydroacyloxylation of Alkynyl Cyclohexadienones2016

    • Author(s)
      澤田和弥、Suman C. Mohanta、竹中和浩、笹井宏明
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学京田辺キャンパス
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] Efficient Synthesis of Spiro-type Chiral Ligands Based on Direct C5 Arylation of Isoxazoles2016

    • Author(s)
      重信匡志、竹中和浩、笹井宏明
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学京田辺キャンパス
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] Asymmetric Synthesis of Spiro-type Chiral Ligands via Catalytic Desymmetrization2016

    • Author(s)
      Bijan M. Chaki、脇田和彦、竹中和浩、滝澤忍、笹井宏明
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学京田辺キャンパス
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] Palladium Enolate Umpolung: Catalytic Cyclative Difunctionalization of Alkynyl Cyclohexadienones Using SPRIX Ligand2016

    • Author(s)
      Mohanta, S. C.; Takenaka, K.; Sasai, H.
    • Organizer
      16th Asian Chemical Congress (16ACC)
    • Place of Presentation
      Dhaka, Bangladesh
    • Year and Date
      2016-03-16
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] パラジウムエノラートの極性転換を基軸とする多官能性カルボニル化合物の効率的合成2016

    • Author(s)
      野本裕也、竹中和浩、澤田和弥、Suman C. Mohanta、笹井宏明
    • Organizer
      第36回有機合成若手セミナー
    • Place of Presentation
      京都薬科大学(京都)
    • Related Report
      2016 Research-status Report
  • [Presentation] Recent Progress of Enantioselective Pd-Catalysis Promoted by Spiro-type Chiral Ligands2015

    • Author(s)
      Mohanta, S. C.; Shigenobu, M.; Wakita, K.; Takenaka, K.; Chaki, B. M.; Sasai, H.
    • Organizer
      The 13th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-13)
    • Place of Presentation
      Kyoto, Japan
    • Year and Date
      2015-11-09
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Catalytic Cyclative Haloacetoxylation of Alkynyl Cyclohexadienones Based on Pd Enolate Umpolung2015

    • Author(s)
      竹中和浩、Suman C. Mohanta、笹井宏明
    • Organizer
      第62回有機金属化学討論会
    • Place of Presentation
      関西大学千里山キャンパス
    • Year and Date
      2015-09-07
    • Related Report
      2015 Research-status Report
  • [Presentation] Catalytic Cyclative Haloacetoxylation Based on Palladium Enolate Umpolung2015

    • Author(s)
      Takenaka, K.; Mohanta, S. C.; Sasai, H.
    • Organizer
      Aachen-Osaka Joint Symposium “Biological and Chemical Methods for Selective Catalysis”
    • Place of Presentation
      Aachen, Germany
    • Year and Date
      2015-09-01
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] パラジウムエノラートの極性転換を基軸とする環化的官能基化反応の開発2015

    • Author(s)
      Suman C. Mohanta、澤田和弥、*新居田恭章、竹中和浩、笹井宏明
    • Organizer
      第35回有機合成若手セミナー
    • Place of Presentation
      京都府立大学下鴨キャンパス
    • Year and Date
      2015-08-01
    • Related Report
      2015 Research-status Report
  • [Presentation] Palladium-Catalyzed Direct C-H Arylation of Isoxazoles at The 5-Position2015

    • Author(s)
      Shigenobu, M.; Takenaka, K.; Sasai, H.
    • Organizer
      18th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS18)
    • Place of Presentation
      Barcelona, Spain
    • Year and Date
      2015-06-28
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research

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Published: 2015-04-16   Modified: 2020-03-30  

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