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Development of Novel Carbon-Carbon Bond Forming Reactions by Allylic gem-Palladium/Metalloid Intermediates

Research Project

Project/Area Number 15K05496
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionUniversity of Toyama

Principal Investigator

Horino Yoshikazu  富山大学, 大学院理工学研究部(工学), 准教授 (30447651)

Project Period (FY) 2015-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2017: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2016: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2015: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywordsパラジウム / ホモアリルアルコール / アリル化反応 / 不斉転写 / アリルパラジウム / 三成分連結反応 / アリルボラン / アリルホウ素 / アリルスズ / カップリング反応 / ホウ素 / スズ
Outline of Final Research Achievements

In this research, we demonstrated the distinct reactivities of allylic gem-palladium/metalloid intermediates. For example, palladium-catalyzed three-component reaction of 3-(n-tributylstannyl)allyl acetates, aldehydes, and organoboranes afforded the (E)-anti-homoallylic alcohols with excellent diastereoselectivity and good to high levels of alkene stereocontrol. Moreover, we developed complementary reaction conditions to provide both (Z)- and (E)-homoallylic alcohols possessing aryl groups at the alkene terminus using a catalyst controlled strategy. The reaction showed good scope and functional group tolerance, many of which could pose difficulties for other transition-metal-catalyzed alkene isomerizations of alkenyl boronates. Thus, the catalytically generated allylic gem-palladium/boryl species promise to serve as synthetically useful intermediates.

Report

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

    (45 results)

All 2018 2017 2016 2015

All Journal Article (7 results) (of which Peer Reviewed: 7 results,  Acknowledgement Compliant: 4 results) Presentation (36 results) (of which Int'l Joint Research: 8 results) Patent(Industrial Property Rights) (2 results)

  • [Journal Article] Controllable Stereoselective Synthesis of (Z)- and (E)-Homoallylic Alcohols Using a Palladium-Catalyzed Three-Component Reaction2017

    • Author(s)
      Horino Yoshikazu、Sugata Miki、Mutsuura Itaru、Tomohara Keisuke、Abe Hitoshi
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 21 Pages: 5968-5971

    • DOI

      10.1021/acs.orglett.7b02979

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-catalyzed diastereoselective synthesis of homoaldol equivalent products2017

    • Author(s)
      Horino Yoshikazu、Sugata Miki、Sugita Tetsu、Aimono Ataru、Abe Hitoshi
    • Journal Title

      Tetrahedron Letters

      Volume: 58 Issue: 22 Pages: 2131-2134

    • DOI

      10.1016/j.tetlet.2017.04.064

    • Related Report
      2017 Annual Research Report 2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Novel Carbon-Carbon Bond Forming Reactions by Allylpalladium Intermediates Possessing Silyl, Boryl, or Stannyl Groups2017

    • Author(s)
      堀野 良和
    • Journal Title

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 75 Issue: 1 Pages: 24-37

    • DOI

      10.5059/yukigoseikyokaishi.75.24

    • NAID

      130005296266

    • ISSN
      0037-9980, 1883-6526
    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] ケイ素,ホウ素,スズ官能基を持つアリルパラジウム中間体を用いた触媒的炭素-炭素結合形成反応2017

    • Author(s)
      堀野良和
    • Journal Title

      有機合成化学協会誌

      Volume: 1 Pages: 24-37

    • NAID

      130005296266

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Facile synthesis of (Z)-anti-homoallylic alcohols from 3-(pinacolatoboryl)allyl alcohols, aldehydes, and triorganoboranes via a palladium-catalyzed three-component reaction2016

    • Author(s)
      Horino, Y; Aimono, A.; Minoshima, N.; Abe, H.
    • Journal Title

      Tetrahedron Letters

      Volume: 57 Issue: 31 Pages: 3561-3564

    • DOI

      10.1016/j.tetlet.2016.06.121

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Palladium-Catalyzed Three-Component Reaction of 3-(n-Tributylstannyl)allyl Acetates, Aldehydes, and Triorganoboranes: An Alternative to the Carbonyl Allylation Using α,γ-Substituted Allylic Tin Reagents2016

    • Author(s)
      Yoshikazu Horino, Miki Sugata, Hitoshi Abe
    • Journal Title

      Advanced synthesis & catalysis

      Volume: 358 Pages: 1023-1028

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Pd-Catalyzed Three-Component Reaction of 3-(Pinacolatoboryl)ally Acetates, Aldehydes, and Organoboranes: A New Entry to Stereoselective Synthesis of (Z)-anti-Homoallylic Alcohols2015

    • Author(s)
      Yoshikazu Horino, Ataru Aimono, Hitoshi Abe
    • Journal Title

      Organic Letters

      Volume: 17 Issue: 11 Pages: 2824-2827

    • DOI

      10.1021/acs.orglett.5b01244

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Pd-Catalyzed Allylation of Aldehydes with Silyl-Substituted Allyl Acetates Proceeding through a Migration of Substituents on Silyl Group2018

    • Author(s)
      Horino Yoshikazu、Mutsuura Itaru、Abe Hitoshi
    • Organizer
      日本化学会 第98春季年会 (2018)
    • Related Report
      2017 Annual Research Report
  • [Presentation] Stereoselective Synthesis of δ-Silyl-Substituted anti-Homoallylic alcohols Using Palladium-Catalyzed Three-Component Reaction2018

    • Author(s)
      Murakami Miki、Horino Yoshikazu、Abe Hitoshi
    • Organizer
      日本化学会 第98春季年会 (2018)
    • Related Report
      2017 Annual Research Report
  • [Presentation] パラジウム触媒を用いた三成分連結反応によるホモアリルアルコールの立体選択的合成法の開発2017

    • Author(s)
      菅田美樹,陸浦至,堀野良和,阿部仁
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応大学日吉キャンパス(神奈川県横浜市)
    • Year and Date
      2017-03-19
    • Related Report
      2016 Research-status Report
  • [Presentation] トリアルキルホウ素をラジカル開始剤とするアルキニルスズへのラジカル付加反応2017

    • Author(s)
      四十物中,杉田哲,堀野良和,阿部仁
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応大学日吉キャンパス(神奈川県横浜市)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] パラジウム触媒用いたビニルケイ素の異性化およびケイ素上の置換基の転位を伴うアリル化反応2017

    • Author(s)
      杉田 哲、堀野 良和、阿部 仁
    • Organizer
      平成29年度北陸地区講演会と研究発表会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Pd-Catalyzed Allylation of Aldehydes with Silyl-Substituted Allyl Acetates Proceeding through a Migration of an Aryl Group of Triarylsilyl Group2017

    • Author(s)
      Sugita Tetsu、Horino Yoshikazu、Abe Hitoshi
    • Organizer
      第三回国際超然シンポジウム
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Controllable Stereoselective Synthesis of (Z)- and (E)-Homoallylic Alcohols using a Palladium-Catalyzed Three-Component Reaction2017

    • Author(s)
      Mutsuura Itaru、Sugata Miki、Horino Yoshikazu、Abe Hitoshi
    • Organizer
      第三回国際超然シンポジウム
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] パラジウム触媒を用いた三成分連結反応によるホモアリルアルコールの立体選択的合成2017

    • Author(s)
      陸浦 至、菅田 美樹、堀野 良和、阿部 仁
    • Organizer
      平成29年度有機合成化学北陸セミナー
    • Related Report
      2017 Annual Research Report
  • [Presentation] Controllable Stereoselective Synthesis of Homoallylic Alcohols by a Palladium-Catalyzed Three-Component Reaction of 3-Pinacolatoboryl Allyl Benzoates, Aldehydes, and Aryl Stannanes2017

    • Author(s)
      Horino Yoshikazu、Sugata Miki、Mutsuura Itaru、Abe Hitoshi
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] パラジウム触媒を用いた三成分連結反応によるホモアリルアルコールの立体選択的合成2017

    • Author(s)
      陸浦 至、菅田 美樹、堀野 良和、阿部 仁
    • Organizer
      テルペンおよび精油化学に関する討論会 (TEAC2017)
    • Related Report
      2017 Annual Research Report
  • [Presentation] パラジウム触媒を用いたホモアルドール等価体の立体選択的合成2017

    • Author(s)
      杉田 哲、菅田 美樹、四十物 中、堀野 良和、阿部 仁
    • Organizer
      テルペンおよび精油化学に関する討論会 (TEAC2017)
    • Related Report
      2017 Annual Research Report
  • [Presentation] パラジウム触媒を用いた三成分連結反応によるホモアリルアルコールの立体選択的合成2017

    • Author(s)
      堀野 良和、陸浦 至、菅田 美樹、阿部 仁
    • Organizer
      第34回有機合成化学セミナー
    • Related Report
      2017 Annual Research Report
  • [Presentation] Controllable Stereoselective Synthesis of Homoallylic Alcohols by a Palladium-Catalyzed Three-Component Reaction of 3-(Pinacolatoboryl)allyl Benzoates, Aldehydes, and Aryl Stannanes2017

    • Author(s)
      Horino Yoshikazu、Mutsuura Itaru、Sugata Miki、Abe Hitoshi
    • Organizer
      19th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 19)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] パラジウム触媒を用いた三成分連結反応によるホモアリルアルコールの立体選択的合成法の開発2016

    • Author(s)
      菅田美樹,陸浦至,堀野良和,阿部仁
    • Organizer
      平成28年度北陸地区講演会と研究発表会
    • Place of Presentation
      福井工業大学(福井県福井市)
    • Year and Date
      2016-11-25
    • Related Report
      2016 Research-status Report
  • [Presentation] トリアルキルホウ素とアルキニルスズの協同効果による新奇ラジカル反応の開発2016

    • Author(s)
      四十物中,堀野良和,阿部仁
    • Organizer
      平成28年度北陸地区講演会と研究発表会
    • Place of Presentation
      福井工業大学(福井県福井市)
    • Year and Date
      2016-11-25
    • Related Report
      2016 Research-status Report
  • [Presentation] σ-アリルパラジウム中間体形成を基軸とする革新的分子変換法の開発2016

    • Author(s)
      堀野良和
    • Organizer
      有機合成化学協会関西支部賞(第14回・平成28年度)
    • Place of Presentation
      大阪科学技術センター(大阪府大阪市)
    • Year and Date
      2016-11-21
    • Related Report
      2016 Research-status Report
  • [Presentation] パラジウム触媒を用いた三成分連結反応によるホモアリルアルコールのZ選択的合成法の開発2016

    • Author(s)
      菅田美樹、陸浦至、堀野良和、阿部仁
    • Organizer
      平成28年度有機合成化学北陸セミナー
    • Place of Presentation
      富山観光ホテル(富山県富山市)
    • Year and Date
      2016-10-07
    • Related Report
      2016 Research-status Report
  • [Presentation] トリアルキルホウ素とアルキニルスズの協同効果による新奇ラジカル反応の開発2016

    • Author(s)
      四十物中,堀野良和,阿部仁
    • Organizer
      平成28年度有機合成化学北陸セミナー
    • Place of Presentation
      富山観光ホテル(富山県富山市)
    • Year and Date
      2016-10-07
    • Related Report
      2016 Research-status Report
  • [Presentation] 3-(トリブチルスタニル)プロパルギルアセテート,アルデヒド,および有機ホウ素反応剤による多成分連結反応2016

    • Author(s)
      四十物中,堀野良和,阿部仁
    • Organizer
      第46回複素環化学討論会
    • Place of Presentation
      金沢歌劇座(石川県金沢市)
    • Year and Date
      2016-09-26
    • Related Report
      2016 Research-status Report
  • [Presentation] 3-トリブチルスタニルプロパルギルアセテート,アルデヒドおよびトリアルキルボランによる多成分連結反応2016

    • Author(s)
      四十物中,堀野良和,阿部仁
    • 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(東京都新宿区)
    • Year and Date
      2016-09-16
    • Related Report
      2016 Research-status Report
  • [Presentation] パラジウム触媒を用いる3-ピナコラトボリルアリルアセテートとアルデヒドの反応2016

    • Author(s)
      堀野 良和・四十物 中・阿部 仁
    • Organizer
      日本化学会 第96春季年会 (2016)
    • Place of Presentation
      同志社大学
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] パラジウム触媒を用いる3-ピナコラトボリルアリルアセテート, アルデヒドおよび有機スズ化合物による三成分連結反応2016

    • Author(s)
      堀野 良和・菅田 美樹・阿部 仁
    • Organizer
      日本化学会 第96春季年会 (2016)
    • Place of Presentation
      同志社大学
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] 3-(トリブチルスタニル)プロパルギルアセテート,アルデヒドおよび有機ホウ素反応剤による多成分連結反応2016

    • Author(s)
      堀野 良和・四十物 中・阿部 仁
    • Organizer
      日本化学会 第96春季年会 (2016)
    • Place of Presentation
      同志社大学
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] Palladium-Catalyzed Multi-Component Reaction of 3-(Tributylstannyl)propargyl Acetates, Aldehydes, and Organoboranes2015

    • Author(s)
      Yoshikazu Horino, Ataru Aimono, Hitoshi Abe
    • Organizer
      環太平洋国際化学会議2015(Pacifichem 2015)
    • Place of Presentation
      ホノルル,ハワイ,アメリカ
    • Year and Date
      2015-12-15
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Palladium-Catalyzed Three-Component Reaction of 3-(Tributylstannyl)ally Acetates, Aldehydes, and Organoboranes: A New Entry to Stereoselective Synthesis of (E)-anti-Homoallylic Alcohols2015

    • Author(s)
      Yoshikazu Horino, Miki Sugata, Hitoshi Abe
    • Organizer
      環太平洋国際化学会議2015(Pacifichem 2015)
    • Place of Presentation
      ホノルル,ハワイ,アメリカ
    • Year and Date
      2015-12-15
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Palladium-Catalyzed Three-Component Reaction of 3-(Tributylstannyl)ally Acetates, Aldehydes, and Organoborane2015

    • Author(s)
      Yoshikazu Horino, Miki Sugata, and Hitoshi Abe
    • Organizer
      第13回国際有機化学京都会議 (IKCOC-13)
    • Place of Presentation
      Rihga Royal Hotel KYOTO
    • Year and Date
      2015-11-09
    • Related Report
      2015 Research-status Report
  • [Presentation] Palladium-Catalyzed Multi-Component Reaction of 3-(Tributylstannyl)propargyl Acetates, Aldehydes, and Organoboranes2015

    • Author(s)
      Yoshikazu Horino, Ataru Aimono, and Hitoshi Abe
    • Organizer
      第13回国際有機化学京都会議 (IKCOC-13)
    • Place of Presentation
      Rihga Royal Hotel KYOTO
    • Year and Date
      2015-11-09
    • Related Report
      2015 Research-status Report
  • [Presentation] Palladium-Catalyzed Three-Component Reaction of 3-(Pinacolatoboryl)ally Acetates, Aldehydes, and Triorganoboranes2015

    • Author(s)
      Yoshikazu Horino, Ataru Aimono, and Hitoshi Abe
    • Organizer
      第13回国際有機化学京都会議(IKCOC-13)
    • Place of Presentation
      Rihga Royal Hotel KYOTO
    • Year and Date
      2015-11-09
    • Related Report
      2015 Research-status Report
  • [Presentation] パラジウム触媒を用いた3-ピナコラトボリルアリルアセテート, アルデヒドおよび有機ホウ素反応剤による三成分連結反応2015

    • Author(s)
      堀野 良和,四十物 中,阿部 仁
    • Organizer
      第108回有機合成シンポジウム2015年【秋】
    • Place of Presentation
      早稲田大学
    • Year and Date
      2015-11-05
    • Related Report
      2015 Research-status Report
  • [Presentation] パラジウム触媒を用いた3-トリブチルスタニルアリルアセテート,アルデヒドおよび有機ホウ素反応剤による三成分連結反応2015

    • Author(s)
      菅田 美樹・堀野 良和・阿部 仁
    • Organizer
      平成27年度有機合成化学北陸セミナー
    • Place of Presentation
      富山観光ホテル
    • Year and Date
      2015-10-02
    • Related Report
      2015 Research-status Report
  • [Presentation] 3-(トリブチルスタニル)プロパルギルアセテート,アルデヒドおよび有機ホウ素反応剤による多成分連結反応2015

    • Author(s)
      四十物中・堀野良和・阿部仁
    • Organizer
      平成27年度有機合成化学北陸セミナー
    • Place of Presentation
      富山観光ホテル
    • Year and Date
      2015-10-02
    • Related Report
      2015 Research-status Report
  • [Presentation] Palladium-Catalyzed Multi-Component Reaction of 3-(Tributylstannyl)propargyl Acetates, Aldehydes, and Organoboranes2015

    • Author(s)
      Yoshikazu Horino, Ataru Aimono, and Hitoshi Abe
    • 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] Palladium-Catalyzed Three-Component Reaction of 3-(Tributylstannyl)ally Acetates, Aldehydes, and Organoboranes2015

    • Author(s)
      Yoshikazu Horino, Miki Sugata, and Hitoshi Abe
    • 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] Palladium-Catalyzed Three-Component Reaction of 3-(Tributylstannyl)ally Acetates, Aldehydes, and Organoboranes: A New Entry to Stereoselective Synthesis of (E)-anti-Homoallylic Alcohols2015

    • Author(s)
      Yoshikazu Horino, Miki Sugata, Hitoshi Abe
    • Organizer
      第3回プロセス化学国際シンポジウム(ISPC)
    • Place of Presentation
      京都国際会館
    • Year and Date
      2015-07-13
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Palladium-Catalysed Three-Componet Reaction of 3-(Pinacolatoboryl)ally Acetates, Aldehydes, and Organoboranes2015

    • Author(s)
      Yoshikazu Horino, Ataru Aimono, Hitoshi Abe
    • Organizer
      第3回プロセス化学国際シンポジウム(ISPC)
    • Place of Presentation
      京都国際会館
    • Year and Date
      2015-07-13
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Palladium-Catalyzed Multi-Component Reaction of 3-(Tributylstannyl)propargyl Acetates, Aldehydes, and Organoboranes2015

    • Author(s)
      Yoshikazu Horino, Ataru Aimono, Hitoshi Abe
    • Organizer
      第3回プロセス化学国際シンポジウム(ISPC)
    • Place of Presentation
      京都国際会館
    • Year and Date
      2015-07-13
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Patent(Industrial Property Rights)] ホモアリルアルコール誘導体の製造方法2016

    • Inventor(s)
      堀野良和
    • Industrial Property Rights Holder
      堀野良和
    • Industrial Property Rights Type
      特許
    • Filing Date
      2016-04-01
    • Related Report
      2016 Research-status Report
  • [Patent(Industrial Property Rights)] ホモアリルアルコール誘導体の製造方法2016

    • Inventor(s)
      堀野良和
    • Industrial Property Rights Holder
      堀野良和
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2016-074757
    • Filing Date
      2016-04-01
    • Related Report
      2015 Research-status Report

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Published: 2015-04-16   Modified: 2019-03-29  

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