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Development of novel double- and single carbonylation processes catalyzed by organotransition metal complexes

Research Project

Project/Area Number 08555231
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section展開研究
Research Field Synthetic chemistry
Research InstitutionWaseda University.

Principal Investigator

YAMAMOTO Akio  Waseda University, Professor, 理工学研究科, 教授 (30016711)

Project Period (FY) 1996 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥15,300,000 (Direct Cost: ¥15,300,000)
Fiscal Year 1998: ¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 1997: ¥4,200,000 (Direct Cost: ¥4,200,000)
Fiscal Year 1996: ¥7,200,000 (Direct Cost: ¥7,200,000)
KeywordsPalladium complex / Carbonylation / Amide / Ester / Anhydride / C-O Activation / Hydrogenation / Aldehyde / パラジウム錯体触媒 / 酸化的カルボニル化反応 / アルコキシカルボニルパラジウム錯体 / カルバモイルパラジウム錯体 / シュウ酸エステル / シュウ酸ジアミド / ジケテン / カルボニル化反応 / ベンジルパラジウム錯体 / 酸化的付加 / 還元的脱離 / フェニルアセチルパラジウム錯体 / アリルアルコール / ベンジルアルコール / 二酸化炭素 / カルボン酸 / ヒドロエステル化 / フェノール
Research Abstract

We investigated here (I) the carbonylation processes of amitnes and alcohols catalyzed by palladium complexes and (2) C-O bond activation by palladium complexes and its application to novel catalytic hydrogenation processes.
Major findings : (a) New direct carbonylation of benzyl alcohol catalyzed by a palladium complex with hydrogen iodide promoter to give phenylacetic acid in excellent yields in aqueous systems was discovered. Application of the carbonylation processes to other arylmethanol analogues provided convenient means to prepare 3-isochromanone, 1, 4-benzeneacetic acid, 2-hydroxybenzeneacetic acid, and 2-naphthaleneacetic acid.
(b)Examination of the reactions of the (phenylacetyl)palladium complexes with secondary amines and alcohols provided supporting evidence for operation of different types of mechanisms for yielding amides and esters. The amide formation is proposed to proceed through coordination of the amine to the palladium center followed by its nucleophilic attack on the acyl group aided by a base. On the other hand, the formation of esters in reaction of acylpalladium with alcohols in the presence of a base is compatible with the reaction mechanism proceeding through an intermediate acyl-alkoxide complex.
(c)Activation of C-O bonds in various oxygen-containing organic compounds such as carboxylic acid anhydrides, carboxylic esters, and diketene by palladium(O) complexes was found to lead to the corresponding products with C-O bond cleavage. Based on these findings, realization of halide-free aldehyde preparation processes by hydrogenation of anhydrides or direct hydrogenation of carboxylic acids in the presence of pivalic anhydride catalyzed by palladium complexes was achieved.

Report

(4 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • 1996 Annual Research Report

Research Products

(39 results)

All Other

All Publications (39 results)

  • [Publications] Masato Sakamoto, Isao Shimizu, and Akio Yamamoto: "Activation of CO and C-N Bonds in Allylic Alchols and Amines by Palladum Complexes Promoted by CO_2 Synthetic Application to Allylation of Nucleophiles, Carbonylation, and Allylamine Disproportionation" Bull.Chem.Soc.Jpn.69. 1065-1078 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Y.Kayaki, I.Shimizu, and A.Yamamoto: "Comparison of the Reactivities of Neutral and Cationic Organopalladium Complexes toward CO, Isocyanides, and Olefins" Bull.Chem.Soc.Jpn.70・4. 917-927 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Y.Kayaki, I.Shimizu, and A.Yamamoto: "Removal of Palladium-Bound Tertiary Phosphine Ligand with Silver(I) Salts to Generate Cationic Monoorganopalladium(II) Complexes Having One Trimethylphosphine Ligand" Bull.Chem.Soc.Jpn.70. 1135-1140 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Y.Kayaki, I.Shimizu, and A.Yamamoto: "Synthesis and Properties of Dimethyl- and Monomethylbis(phosphite)palladium(II) Complexes" Bull.Chem.Soc.Jpn.70. 1141-1147 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Y.-S.Lin and A.Yamamoto: "Palladium-Catalyzed Carbonylation of Benzyl Alchol and Its Analogs Promoted by HI in Aqueous Systems" Tetrahedron Lett.38・21. 3747-3750 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Yong-Shou Lin and Akio Yamamoto: "Studies Relevant to Palladium-Catalyzed Carbonylation Processes. Mechanisms of Formation of Esters and Amides from Benzylpalladium and (Phenylacetyl)palladium Complexes on Reactions with Alcohols and Amines" Organometallics. 17. 3466-3478 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Y.-S.Lin and A.Yamamoto: "Direct Carbonylation of Benzyl Alchols and Its Analogs Catalyzed by Palladium and HI in Aqueous Systems and Mechanistic Studies" Bull.Chem.Soc.Jpn.71. 723-734 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Kazuhiro Nagayama, Isao Shimizu, and Akio Yamamoto: "Direct Hydrogenation of Carboxylic Acids to Corresponding Aldehydes Catalyzed by Palladium Complexes in the Presence of Pivalic Anhydride" Chem.Lett.1143-1144 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Kazuhiro Nagayama, Isao Shimizu, and Akio Yamamoto: "Oxidative Addition of Aryl and Benzyl Trifluoroacetates to Zerovalent Palladium Complexes with Two Modes of C-O Bond Cleavage Processes" Bull.Chem.Soc.Jpn.(掲載予定).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Kazuhiro Nagayama, Futoshi Kawataka, Masato Sakamoto, Isao Shimizu, and Akio Yamamoto: "Preparation of Acyl(carboxylato)palladium(II) Complexes by C-O Bond Cleavage of Carboxylic Anhydride on Interaction with Palladium(0) Complexes. Catalytic Hydrogenation of Carboxylic Anhydrides to Aldehydes by Palladium Complexes" Bull.Chem.Soc.Jpn.72. 573-580 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Yamamoto: "Insertion Chemistry into Metal-Carbon Bonds" J.Chem.Soc., Dalton Trans.(掲載予定).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Edited by Shun-Ichi Murahashi, Yoshihiko Moro-oka, Akio Yamamoto: "Reactive Organometallics" KODANSHA, Tokyo. 327-342 343-346 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Akio Yamamoto and Yong-Shou Lin: "Activation of C-O Bonds. Stoichiometric and Catalytic Reactions" Topics in Organometallic Chemistry. Springer. (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 榧木啓人、 山本明夫: "触媒活性種モデルとしての有機パラジウム錯体の合成と反応性" 有機合成化学協会誌. 56・2. 96-106 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Masato Sakamoto, Isao Shimizu, and Akio Yamamoto: ""Activation of C-O and C-N Bonds in Allylic Alchols and Amines by Palladium Complexes Promoted by CO_2. Synthetic Application to Allylation of Nucleophiles, Carbonylation, and Allylamine Disproportionation"" Bull.Chem.Soc.Jpn.69. 1065-1078 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Yoshihito Kayaki, Isao Shimizu, and Akio Yamamoto: ""Comparison of the Reactivities of Neutral and Cationic Organopalladium Complexes toward CO,Isocyanides, and Olefins"" Bull.Chem.Soc.Jpn.70. 917-927 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Yoshihito Kayaki, Isao Shimizu, and Akio Yamamoto: ""Removal of Palladium-Bound Tertiary Phosphine Ligand with Silver (I) Salts to Generate Cationic Monoorganopalladium (II) Complexes Having One Trimethylphosphine Ligand"" Bull.Chem.Soc.Jpn.70. 1135-1140 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Yoshihito Kayaki, Isao Shimizu, and Akio Yamamoto: ""Synthesis and Properties of Dimethyl- and Monomethylbis (phosphite) palladium (II) Complexes"" Bull.Chem.Soc.Jpn.70. 1141-1147 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Yong-Shou Lin and Akio Yamamoto: ""Palladium-Catalyzed Carbonylation of Benzyl Alcohol and Its Analogs Promoted by HI in Aqueous Systems"" Tetrahedron Lett.38. 3747-3750 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Yong-Shou Lin and Akio Yamamoto: ""Direct Carbonylation of Benzyl Alcohol and Its Analogs Catalyzed by Palladium and HI in Aqueous Systems and Mechanistic Studies"" Bull.Chem.Soc.Jpn.71. 723-734 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Yong-Shou Lin and Akio Yamamoto: ""Studies Relevant to Palladium-Catalyzed Carbonylation Processes. Mechanisms of Formation of Esters and Amides from Benzylpalladium and (Phenylacetyl) Palladium Complexes on Reactions with Alcohols and Amines"" Organometallics. 17. 3466-3478 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Kazuhiro Nagayama, Isao Shimizu, and Akio Yamamoto: ""Direct Hydrogenation of Carboxylic Acids to Corresponding Aldehydes Catalyzed by Palladium Complexes in the Presence of Pivalic Anhydride"" Chem.Lett.1143-1144 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Kazuhiro Nagayama, Isao Shimizu, and Akio Yamamoto: ""Oxidative Addition of Aryl and Benzyl Trifluoroacetates to Zerovalent Palladium Complexes with Two Modes of C-O Bond Cleavage Processes"" Bull.Chem.Soc.Jpn.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Kazuhiro Nagayama, Futoshi Kawataka, Masato Sakamoto, Isao Shimizu, and Akio Yamamoto: ""Preparation of Acyl (carboxylato) palladium (II) Complexes by C-O Bond Cleavage of Carboxylic Anhydride on Interaction with Palladium (0) Complexes. Catalytic Hydrogenation of Carboxylic Anhydrides to Aldehydes by Palladium Complexes"" Bull.Chem.Soc.Jpn.72. 573-580 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Yamamoto: ""Insertion Chemistry into Metal-Carbon Bonds"" J.Chem.Soc., Dalton Trans.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Akio Yamamoto: ""Catalysis with Reactive Organometallics"" Reactive Organometallics, ed by Shun-Ichi Murahashi, Yoshihiko Moro-oka, and Akio Yamamoto. KODANSHA. 327-342 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Akio Yamamoto: ""Studies of Fundamental Processes Involving Organotransition Metal Complexes and Application to Organic Synthesis"" Reactive Oeganometallics, ed by Shun-Ichi Murahashi, Yoshihiko Moro-oka, and Akio Yamamoto. KODANSHA. 343-346 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Akio Yamamoto and Yong-Shou Lin: ""Activation of C-O Bonds.Stoichiometric and Catalytic Reactions"" Topics in Organometallic Chemistry. Springer, (in press.).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Yong-Shou Lin and Akio Yamamoto: "Studies Relevant to Palladium-Catalyzed Carbonylation Processes.Mechanisms of Formation of Esters and Amides from Benzylpalladium and(Phenylacetyl)palladium Complexes on Reactions with Alcohols and Amines" Organometallics. 17. 3466-3478 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Kazuhiro Nagayama, Isao Shimizu, and Akio Yamamoto: "Oxidative Addition of Aryl and Benzyl Trifluoroacetates to Zerovalent Palladium Complexes with Two Modes of C-O Bond Cleavage Processes" Bull.Chem.Soc.Jpn.(掲載予定).

    • Related Report
      1998 Annual Research Report
  • [Publications] Kazuhiro Nagayama, Futoshi Kawataka, Masato Sakamoto, Isao Shimizu, and Akio Yamamoto: "Preparation of Acyl(carboxylato)palladium(II)Complexes by C-O Bond Cleavage of Carboxylic Anhydride on Interaction with Palladium(0)Complexes.Catalytic Hydrogenation of Carboxylic Anhydrides to Aldehydes by Palladium Complexes" Bull.Chem.Soc.Jpn.(掲載予定).

    • Related Report
      1998 Annual Research Report
  • [Publications] A.Yamamoto: "Insertion Chemistry into Metal-Carbon Bonds" J.Chem.Soc., Dalton Trans.(掲載予定).

    • Related Report
      1998 Annual Research Report
  • [Publications] Edited by Shun-Ichi Murahashi, Yoshihiko Moro-oka, Akio Yamamoto: "Reactive Organometallics" KODANSHA, Tokyo. (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Akio Yamamoto and Yong-Shou Lin: "Activation of C-O Bonds.Stoichiometric and Catalytic Reactions" Topics in Organometallic Chemistry. Springer. (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Y.-S. Lin and A. Yamamoto: "Palladium-Catalyzed Carbonylation of Benzyl Alchol and Its Analogs Promoted by HI in Aqueous Systems" Tetrahedron Lett.38・21. 3747-3750 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y. Kayaki, I. Shimizu, and A. Yamamoto: "Comparison of the Reactivities of Neutral and Cationic Organopalladium Complxes toward CO, Isocyanides, and Olefins" Bull. Chem. Soc. Jpn.70・4. 917-927 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.-S. Lin and A. Yamamoto: "Direct Carbonylation of Benzyl Alchols and Its Analogs Catalyzed by Palladium and HI in Aqueous Systems and Mechanistic Studies" Bull. Chem. Soc. Jpn.71(掲載予定). (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] 榧木啓人、山本明夫: "触媒活性種モデルとしての有機パラジウム錯体の合成と反応性" 有機合成化学教会誌、. 56・2(掲載予定). (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] M.Sakamoto,I.Shimizu,and A.Yamamoto: "Activation of C-O and C-N Bonds in Allylic Alcohols and Amines by Palladium Complexes Promoted by CO_2 Synthetic Applications to Allylation of Neucleophiles,Carbonylation,and Allylamine Disproportionation" Bull.Chem.Soc.Jpn.69・4. 1065-1078 (1996)

    • Related Report
      1996 Annual Research Report

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Published: 1996-03-31   Modified: 2016-04-21  

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