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Novel Approaches for Carbonylation by the Cooperative Control of Radical and Metal Species

Research Project

Project/Area Number 23350045
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionOsaka Prefecture University

Principal Investigator

RYU Ilhyong  大阪府立大学, 理学(系)研究科(研究院), 教授 (80210821)

Co-Investigator(Kenkyū-buntansha) FUKUYAMA Takahide  大阪府立大学, 理学系研究科, 准教授 (60332962)
UEDA Mitsuhiro  大阪府立大学, 理学系研究科, 助教 (60566298)
Project Period (FY) 2011-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥17,810,000 (Direct Cost: ¥13,700,000、Indirect Cost: ¥4,110,000)
Fiscal Year 2013: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2012: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2011: ¥6,890,000 (Direct Cost: ¥5,300,000、Indirect Cost: ¥1,590,000)
Keywordsラジカル / カルボニル化 / 非対称ケトン / アシルリチウム / C-Hカルボニル化 / 光照射 / パラジウム / 一酸化炭素 / アシルラジカル / アシルパラジウム / 活性種複合系反応 / アルキルアリールケトン / カルバモイルアセテート / 光触媒 / デカタングステート / ジエステル / β-ケトアミド / パラジウムラジカル
Outline of Final Research Achievements

Carbon monoxide is among important feedstock. In this study we have developed new carbonylation methods, which are based on the power of the strategy employing controlled dual species, such as radical and palladium species to achieve new carbonylation methods. Diesters were obtained in good yields by four-component coupling reactions comprising α-iodo esters, alkenes, CO, and alcohols under photo-irradiation conditions in the presence of Pd as a catalyst. Similarly the three-component reaction comprising α-iodo esters, CO, and amines gave good yields of β-keto amides with incorporation of CO. Unsymmetrical ketones, such as alkyl aryl ketones, were synthesized from iodoalkanes, CO and arylboronic acids in good yields. Polyoxodecatungstate anion was used as a photocatalyst to achieve a new type of C-H carbonylation reaction. Flow carbonylation was also examined successfully to affect high-yield trapping of CO by organolithium compounds.

Report

(4 results)
  • 2014 Final Research Report ( PDF )
  • 2013 Annual Research Report
  • 2012 Annual Research Report
  • 2011 Annual Research Report
  • Research Products

    (34 results)

All 2014 2013 2012 2011

All Journal Article (13 results) (of which Peer Reviewed: 13 results) Presentation (21 results) (of which Invited: 2 results)

  • [Journal Article] Carbonylation in Microflow : Close Encounters of CO and Reactive Species2014

    • Author(s)
      Fukuyama, T.; Totoki, T.; Ryu, I.
    • Journal Title

      Green Chemistry

      Volume: 16 Issue: 4 Pages: 2042-2050

    • DOI

      10.1039/c3gc41789a

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] One-pot synthesis of cyanohydrin derivatives from alkyl bromides via incorporation of two one-carbon components by consecutive radical/ionic reactions2014

    • Author(s)
      Smino, S.; Fusano, A.; Okai, H.; Fukuyama, T.; Ryu, I.
    • Journal Title

      Beilstein J. Org. Chem.

      Volume: 10 Pages: 150-154

    • DOI

      10.3762/bjoc.10.12

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Alkyl Aryl Ketones by Pd/Light Induced Carbonylative Cross-Coupling of Alkyl Iodides and Arylboronic Acids2013

    • Author(s)
      Sumino, S.;Ui, T.; Ryu, I.
    • Journal Title

      Org. Lett.

      Volume: 15 Pages: 3142-3145

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Modernized Low Pressure Carbonylation Methods in Batch and Flow Employing Common Acids as a CO Source2013

    • Author(s)
      Brancour, C.; Fukuyama, T.; Mukai, Y.; Skrydstrup, T.; Ryu, I.
    • Journal Title

      Org. Lett.

      Volume: 15 Pages: 2794-2797

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Efficient C-H/C-N and C-H/C-CO-N Conversion via Decatungstate-Photoinduced Alkylation of Diisopropyl Azodicarboxylate2013

    • Author(s)
      Ryu, I.; Tani, A.; Fukuyama, T.; Ravelli, D.; Montanaro, S.; Fagnoni, M.
    • Journal Title

      Org. Lett.

      Volume: 15 Pages: 2554-2557

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Free-Radical-Mediated [2+2+1] Cycloaddition of Acetylenes, and CO Leading to Five-Membered a,b-Unsaturated Lactams2013

    • Author(s)
      Fukuyama, T.; Nakashima, N.; Okada, T.; Ryu, I
    • Journal Title

      J. Am. Chem. Soc

      Volume: 135 Issue: 3 Pages: 1006-1009

    • DOI

      10.1021/ja312654q

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Carbamoylacetate from α-Iodoacetate, CO, and Amines under Pd/Light Combined Conditions2012

    • Author(s)
      Sumino, S.; Fusano, A.; Fukuyama, T.; Ryu, I.
    • Journal Title

      Synlett

      Volume: 23 Issue: 09 Pages: 1331-1334

    • DOI

      10.1055/s-0031-1290690

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Pd/Light-Accelerated Atom-Transfer Carbonylation of Alkyl Iodides: Application in Multicomponent Coupling Processes Leading to Functionalized Carboxylic Acid Derivatves2012

    • Author(s)
      Fusano, A.; Sumino, S.; Nishitani, S.; Inoue, T.; Morimoto, K.; Fukuyama, T.; Ryu, I
    • Journal Title

      Chem. Eur. J

      Volume: 18 Issue: 30 Pages: 9415-9422

    • DOI

      10.1002/chem.201200752

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Rh-Catalyzed [5+1] and [4+1] Cycloaddition Reaction of 1,4-Enyne Esters with CO. Shortcut to Functionalized Resorcinols and Cyclopentenones2012

    • Author(s)
      Fukuyama, T.; Ohta, Y.; Brancour, C.; Miyagawa, K.; Ryu, I.; Dhimane, A.; Fensterbank, L.; Malacria, M.
    • Journal Title

      Chem. -Eur. J.

      Volume: 18 Issue: 23 Pages: 7243-7247

    • DOI

      10.1002/chem.201200045

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Carbamoylacetates from α-Iodoesters, CO, and Amines under Pd/Light Combined Conditions2012

    • Author(s)
      Sumino, S.; Fusano, A.; Fukuyama, T.; Ryu, I.
    • Journal Title

      Synlett

      Volume: (in press)

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Rh-Catalyzed [5+1] and [4+1] Cycloaddition Reaction of 1,4-Enyne Esters with CO. Shortcut to Functionalized Resorcinols and Cyclopentenones2012

    • Author(s)
      Fukuyama, T.; Ohta, Y.; Brancour, C.; Miyagawa, K.; Ryu, I.; Dhimane, A.; Fensterbank, L.; Malacria, M.
    • Journal Title

      Chem.Eur.J.

      Volume: (in press)

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Iron-catalyzed Decarbonylation Reaction of Aliphatic Carboxylic Acids Leading to α-Olefins2012

    • Author(s)
      Maetani, S.; Fukuyama, T.; Suzuki, N.; Ishihara, D.; Ryu, I.
    • Journal Title

      Chem.Commun.

      Volume: 48 Issue: 19 Pages: 2552-2554

    • DOI

      10.1039/c2cc18093f

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Vicinal C-Functionalization of Alkenes. Pd/Light-Induced Multicomponent Coupling Reactions Leading to Functionalized Esters and Lactones2011

    • Author(s)
      Fusano, A.; Sumino, S.; Fukuyama, T.; Ryu, I.
    • Journal Title

      Org.Lett.

      Volume: 13 Issue: 8 Pages: 2114-2117

    • DOI

      10.1021/ol200536h

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Presentation] 一酸化炭素およびスルホニルオキシムエーテルをダブルC-1ユニットとしたラジカルカスケード反応2014

    • Author(s)
      隅野修平・福山高英・笹野美香・柳 日馨・JACQUET Antoine・ROBERT Frederic・LANDAIS Yannick
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      愛知県
    • Related Report
      2013 Annual Research Report
  • [Presentation] Pd触媒存在下、α-ヨードエステル、一酸化炭素、アリールボロン酸からのβ-ケトエステル合成2014

    • Author(s)
      隅野修平・宇井隆人・柳 日馨
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      愛知県
    • Related Report
      2013 Annual Research Report
  • [Presentation] 光触媒によるラジカル的C-H/C-C変換反応における位置選択性2014

    • Author(s)
      岡田めぐみ・福山高英・柳 日馨
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      愛知県
    • Related Report
      2013 Annual Research Report
  • [Presentation] 2-リチオビフェニルのカルボニル化によるフルオレノール合成2014

    • Author(s)
      福山高英・十時丈典・柳 日馨
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      愛知県
    • Related Report
      2013 Annual Research Report
  • [Presentation] A Novel Synthesis of Alkyl Aryl Ketones from Alkyl Iodides, CO, and Arylboronic Acids2013

    • Author(s)
      Shuhei Sumino, Takahito Ui, and Ilhyong Ryu
    • Organizer
      The 8th International Symposium on Integrated Synthesis (ISIS-8)
    • Place of Presentation
      奈良県
    • Related Report
      2013 Annual Research Report
  • [Presentation] Synthesis of N-Heterocycles by Radical Annulation Approaches2013

    • Author(s)
      Ilhyong Ryu
    • Organizer
      11th International Symposium on Organic Reactions (ISOR-11)
    • Place of Presentation
      Taiwan
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Generation and Carbonylation of α-Silyl-Substituted arbanions Using a Continuous Microflow System2013

    • Author(s)
      Takahide Fukuyama, Takenori Totoki, and Ilhyong Ryu
    • Organizer
      10th International Symposium on Carbanion Chemistry (ISCC-10)
    • Place of Presentation
      京都府
    • Related Report
      2013 Annual Research Report
  • [Presentation] Synthesis of Alkyl Aryl Ketones from Alkyl Iodides, Arylboronic Acids and Carbon Monoxide under Pd/Light Conditions2013

    • Author(s)
      Shuhei Sumino, Takahito Ui, and Ilhyong Ryu
    • Organizer
      60th Symposium on Organometallic Chemistry
    • Place of Presentation
      東京都
    • Related Report
      2013 Annual Research Report
  • [Presentation] Generation and Carbonylation of Silyl-Substituted Carbanions Using a Flow Microreactor2013

    • Author(s)
      Takahide Fukuyama, Takenori Totoki, Ilhyong Ryu
    • Organizer
      3rd Asia-Pacific Chemical and Biological Microfluidics Conferences
    • Place of Presentation
      Korea
    • Related Report
      2013 Annual Research Report
  • [Presentation] Radical Hydroxymethylation of Alkyl and Aryl Iodides Using NHC-BH3 and CO2013

    • Author(s)
      Takuji Kawamoto, Takuma Okada, Dennis P. Curran, Ilhyong Ryu
    • Organizer
      The 6th Pacific Symposium on Radical Chemistry (PSRC-6)
    • Place of Presentation
      Canada
    • Related Report
      2013 Annual Research Report
  • [Presentation] アルキリデンシクロプロパンと一酸化炭素と臭化アリルによる三成分連結型ラジカル反応2013

    • Author(s)
      吉方孝至・柳 日馨
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      滋賀県
    • Related Report
      2012 Annual Research Report
  • [Presentation] デカタングステート触媒によるケトンとオレフィンの位置選択的C-C結合形成反応2013

    • Author(s)
      岡田めぐみ・柳 日馨
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      滋賀県
    • Related Report
      2012 Annual Research Report
  • [Presentation] 連続フローマイクロ系によるシリルアリルリチウムの発生とカルボニル化2013

    • Author(s)
      福山高英・十時丈典・柳 日馨
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      滋賀県
    • Related Report
      2012 Annual Research Report
  • [Presentation] アルキルヨウ素化物と一酸化炭素とアリールボロン酸からのケトン合成2013

    • Author(s)
      隅野修平・宇井隆人・柳 日馨
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      滋賀県
    • Related Report
      2012 Annual Research Report
  • [Presentation] Under Photoirradiation, the Palladium Dimer Complex Having Pd-Pd Bond Mediated Radical Bond Forming Reactions2012

    • Author(s)
      Shuhei Sumino, Takahide Fukuyama, and Ilhyong Ryu
    • Organizer
      59th Symposium on Organometallic Chemistry
    • Place of Presentation
      大阪府
    • Related Report
      2012 Annual Research Report
  • [Presentation] Multi-Component Coupling Reaction Processes by Pd/Light Accelerated Atom Transfer Carbonylation of Alkyl Iodides2012

    • Author(s)
      Ilhyong Ryu
    • Organizer
      95th Canadian Chemistry Conference and Exhibition
    • Place of Presentation
      Calgary
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] パラジウム/光系におけるアルキルヨウ素化物のカルボニル化反応の機構的考察2012

    • Author(s)
      房野暁・隅野修平・岡田めぐみ・福山高英・柳日馨
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      神奈川
    • Related Report
      2011 Annual Research Report
  • [Presentation] Pd/Light Induced Four-Component Coupling Reactions Leading to Function alized Esters via Vicinal C-Functionalization of Alkenes2011

    • Author(s)
      Akira Fusano, Shuhei Sumino, Takahide Fukuyama, Ilhyong Ryu
    • Organizer
      5^<th> Pacific Symposium on Radical Chemistry
    • Place of Presentation
      和歌山
    • Related Report
      2011 Annual Research Report
  • [Presentation] Annulative Three-Component Coupling Reaction Based on Pd/Light-Induced Atom Transfer Carbonylation2011

    • Author(s)
      Shuhei Sumino, Akira Fusano, Takahide Fukuyama, Ilhyong Ryu
    • Organizer
      5^<th> Pacific Symposium on Radical Chemistry
    • Place of Presentation
      和歌山
    • Related Report
      2011 Annual Research Report
  • [Presentation] Atom-Economical Synthesis of Unsymmetrical Ketones via Photocatalyzed C-H Activation of Alkanes and Coupling with CO and Electorophilic Alkenes2011

    • Author(s)
      Ilhyong Ryu, Akihiro Tani, Davide Ravelli, Maurizio Fagnoni, Takahide Fukuyama, Angelo Albini
    • Organizer
      5^<th> Pacific Symposium on Radical Chemistry
    • Place of Presentation
      和歌山
    • Related Report
      2011 Annual Research Report
  • [Presentation] Free Radical Mediated Three-Coupling Reaction Comprising Alkynes, Imines, and CO Leading to Five-Memberd Unsaturated Lactams2011

    • Author(s)
      Takuma Okada, Ilhyong Ryu, Takahide Fukuyama
    • Organizer
      5^<th> Pacific Symposium on Radical Chemistry
    • Place of Presentation
      和歌山
    • Related Report
      2011 Annual Research Report

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Published: 2011-04-06   Modified: 2019-07-29  

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