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1991 Fiscal Year Final Research Report Summary

Synthesis, Properties and Chemical Functions of Group 8 Transition Metal Nitrosyl Complexes

Research Project

Project/Area Number 02640403
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionUniversity of Osaka Prefecture

Principal Investigator

OTSUJI Yoshio  Univ. of Osaka Prefecture College of Engineering Dept. of Applied Chemistry Professor, 工学部, 教授 (20081341)

Project Period (FY) 1990 – 1991
Keywordseta^3-Allyliron Complex / Nitrosyliron Complex / Allyl Cation Equivalent / Allyl Anion Equivalent / alpha-Acylcarbocation Equivalent / alpha-Acylcarbanion Equivalent / beta-Acylcarbocation Equivalent / beta-Acylcarbanion Equivalent
Research Abstract

The title subjects have been studied with the intention of developing new synthetic reactions by utilizing characteristic chemical properties of newly synthesized complexes. The special emphasis has been placed on the chemistry of eta^3-allylnitrosyliron complexes. The major outcomes of this research can be summarized as follows :
1. (eta^3-Allyl)Fe(CO)_2NO complexes 1 can be synthesized efficiently from allylic halides, (eta^3-1-trimethylsiloxyallyl)Fe(CO)_2NO complexes 2 from alpha, beta-unsaturated carbonyl compounds, (eta^3-2-trimethylsiloxyallyl)Fe(CO)_2NO complexes 3 from alpha-halocarbonyl compounds, [eta^3-1-(acylmethyl)-allyl]Fe(CO)_2NO complexes 4 from 1, 3-dienes, and (eta^3-1-acetoxyallyl)Fe(CO)_2NO complexes 5 from alkenyloxiranes by using Bu_4N^+[Fe(CO)_3NO]^- as a reagent. 2. All these complexes react with both of carbon electrophiles and carbon nucleophiles with a high regio-selectivity. 3. These complexes exhibit interesting reactivity features. The detailed studies have shown that the complexes 1 can be utilized as synthetically equivalent synthons for both of allylcations and allylanions, the complexes 2 as those for both of beta-acylcarbocations and beta-acylcarbanions, the complexes 3 as those for both of alpha-acylcarbocations and alpha-acylcarbanions, the complexes 4 as intermediates for 1, 4-functionalization of 1, 3-dienes, and the complexes 5 as intermediates for the synthesis of multifunctionalized alcohols. 4. The allylic ligands of 1, 2, 3, and 4 undergo a conjugate addition to alpha, beta-unsaturated carbonyl compounds, affording a variety of multifunctionalized compounds with a high selectivity. 5. The reactions of the iron complexes with carbon electrophiles and carbon nucleophiles proceed via two different, distinctive stereochemical courses, and the regio- and stereo-selectivities of both the reactions are generally high.

  • Research Products

    (22 results)

All Other

All Publications (22 results)

  • [Publications] 中西 三郎: "Synthesis of Pyrrole Derivatives from 5,6ーDihydroー4Hー1,2ーoxazines by Use of Fe_3(CO)_<12>." Bull.Chem.Soc.Jpn.63. 3595-3600 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 中西 三郎: "A New Route to bis(μーCycloalkylideneamido)hexaーcarbonyldiron Complexes via a Reductive Fission of =NーO Bond by Fe_3(CO)_<12>." Chem.Express. 5. 73-76 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 伊藤 詣二: "Redox Reaction of Aromatic Aldehydes with Fe_3(CO)_<12>." Bull.Chem.Soc.Jpn.64. 118-122 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 伊藤 詣二: "Preparation and Reactivities or(η3ー1ーand 2ーTrimethylsiloxyallyl)Fe(CO)_2NO Complexes.Intermediates Functioning as Equivalents of βーand αーAcyl Carbocations and and Acvl Carbanions." Bull.Chem.Soc.Jpn.64. 2965-2977 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 大辻 吉男: "有機金属活性種の開発とその合成化学的展開." 有機合成化学協会誌. 49. 2-15 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 中西 三郎: "Structural Features of(η^3ーallyl)Fe(CO)(NO)PR_3 Complexes as Studied by VariableーTemperature NMR and FTーIR Spectroscopies." Chem.Lett.

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 伊藤 詣二: "アルケニルオキシランの開環による(η^3ーアリル)Fe(CO)_2NO錯体の合成と反応性" 日本化学会第59春季年会講演予稿集,Chem.Lett. II. 1374 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 伊藤 詣二: "Conjugated Addition of Allylic Groups to α,βーUnsaturated Carbonyl Compounds via(η^3ーAllyl)Fe(CO)_2NO Complexes" 第38回有機金属化学講論会講演予稿集Bull.Chem.Soc.Jpn.397-399 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 中西 三郎: "Ligand Substitution Reaction of Dinuclear Iron Carbonyl Complexes(η^5ーRC_5H_4)Fe_2(CO)_4 with Isonitriles" 第37回有機金属化学討論会講演予稿集Chem.Lett.82-84 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 中西 三郎: "Preparation,Resolution and Properties of(η^4ーCH_3CH=CHCH=CHCOX)Fe(CO)_3 Complexes" 日本化学会第62秋季年会講演予稿集Chem.Lett.II. 696 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 中西 三郎: "カチオン性不飽和カルベン鉄錯体の合成と化学的特性" 日本化学会第63春季年会Bull.Chem.Soc.Jpn.(1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S. Nakanishi et al: ""Synthesis of Pyrrole Derivatives from 5, 6-Dihydro-4H-1, 2-oxazines by Use of Fe_3(CO)_<12>"." Bull Chem. Soc. Jpn.63. 3595-3600 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S. Nakanishi et al: ""A New Route to bis (mu-Cycloalkylideneamido) hexacarbonyldiiron Complexes via a Reductive Fission of =N-O Bond by Fe_3(CO)_<12>"." Chem. Express. 5. 73-76 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Itoh et al: ""Redox Reaction of Aromatic Aldehyses with Fe_3(CO)_<12>"." Bull. Chem. Soc. Jpn.64. 118-122 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Itoh et al: ""Preparation and Reactivities of (eta^3-1-and 2-Trimethylsiloxyallyl)Fe(CO)_2NO Complexes. Intermediates Functioning as Equivalents of beta-and alpha Acyl Carbocations and Acyl Carbanions." Bull. Chem. Soc. Jpn.64. 2965-2977 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Otsuji: ""Generation of Reactive Species of Organometallic Compounds and Their Applications in Organic Synthesis"." Yuki Gousei Kagaku Kyoukai Shi. 49. 2-15 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S. Nakanishi et al: ""Structural Feature of (eta^3-allyl)Fe(CO)(NO)PR_3 Complexes as Studied by Variable-Temperature NMR and FT-IR Spectroscopies"." Chem. Lett.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Itoh et al: ""Synthesis of (eta^3-Allyl)Fe(CO)_2NO Complexes via Ring-Opening of Alkenyloxiranes and Their Reactivity"." 49th National Meeting of the Chemical Society of Japan, April, 1990, Abstr. II. 1374

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Itoh et al: ""Conjugated Addition of Allylic Group to alpha, beta-Unsaturated Carbonyl Compounds via (eta^3-Allyl)Fe(CO)_2NO Complexes"." 38th Symposium on Organometallic Chemistry, Nov., 1991, Abstr.397-399

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S. Nakanishi et al: ""Ligand Substitution Reaction of Dinuclear Iron Carbonyl Complexes (eta^5-RC_5H_4)_2Fe_2(CO)_4 with Isonitriles"." 37th Symposium on Organometallic Chemistry, Nov., 1990, Abstr.82-84

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S. Nakanishi et al: ""Preparation, Resolution and Properties of (eta^4-CH_3CH=CHCH=CHCOX)Fe(CO)_3 Complexes"." 62nd National Meeting of the Chemical Society of Japan, Sept., 1991, Abstr. II. 696

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S. Nakanishi et al: ""Preparation and Properties of Cationic Iron Unsaturated Carbene Complexes"." 63rd National Meeting of Chemical Society of Japan, March. (1992)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1993-03-16  

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