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CYCLIZATION BY AN INTRAMOLECULAR ALLENE INSERTION INTO π-ALLYLIC PALLADIUMS AND BY CARBONYLATION

Research Project

Project/Area Number 10650857
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionSCIENCE UNIVERSITY OF TOKYO IN YAMAGUCHI

Principal Investigator

YAMAMOTO Kenji  SCI. UNIV. TOKYO IN YAMAGUCHI, DEPT. MATERIALS SCI & ENG. PROFESSOR, 基礎工学部, 教授 (80025999)

Co-Investigator(Kenkyū-buntansha) DOI Takayuki  TOKYO INST. TECH., DEPT. CHEM. ENG. RESEARCH ASSOCIATE, 工学部, 助手 (90212076)
KAWAMAMI Yukio  SCI. UNIV. TOKYO IN YAMAGUCHI, DEPT. MATERIALS SCI & ENG. RESEARCH ASSOCIATE, 基礎工学部, 助手 (50289302)
Project Period (FY) 1998 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 1999: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1998: ¥2,500,000 (Direct Cost: ¥2,500,000)
KeywordsPalladium Catalyst / π-Allylpalladium / Carbonylation / Carbin-carbon bond / Allene insertion / Five-membered ring / Domino / Capnellene / 一酸化炭素
Research Abstract

On a line of research program of the cyclization strategy which rely on an intramolecular alkene insertion into π-allylic palladium intermediate in acetic acid as a necessary solvent, we have also found the palladium(0)-catalyzed, domino-type insertion and Carbonylation to take place by the use of an allene moiety tethered with an allylic acetate as the substrate, the cyclization being highly controlled in terms of both regio- and stereoselectivity : I. E., the π-allylic palladium intermediate, formed from oxidative addition of certain allylic acetate having an allene counterpart with palladium(0) catalyst under a carbon monoxide atmosphere, undergoes facile allene insertion to give either cyclized (five-membered ring) σ-vinylic palladium intermediate or another π-allylic palladium intermediate, which constitutes also a five-membered ring system, the latter two intermediates being followed by carbonylation, to afford five-membered condensed ring systems with carbonyl functionalities. Thus, the strategy provides a unique procedure for condensed polycycles.
As one of recent results, we have prepared a four-ring-condensed five-membered ring systems in an appreciable yield by the palladium(0)-catalyzed successive (domino) insertion-carbonylation staring from 5-alkenyl-1, 6, 7-octatrienyl esters, such as 5-(3-butenyl)-5-methyl-1, 6, 7-octarien-3-yl acetate and 5, 8-dimethyl-5-(1, 2-propadienyl)-2, 8-nonadienyl acetate. It is worthy of note that the present catalytic reaction creates six carbon-carbon bonds in one operation. An attempted shortstep synthesis of capnellene and related capnellenol, one of tricyclic sesquiterpenes, as undertaken by way of the present domino-type cyclization-carbonylation with concomitant introduction of an angular methyl group.

Report

(3 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • Research Products

    (11 results)

All Other

All Publications (11 results)

  • [Publications] T.Doi: "Palladium(0)-Catalyzed Domino Cyclization-Carbonylation of Alkenyl-Allenyl-Allylic Acetate"Bull.Chem.Soc.Jpn.. 71,^#12. 2929-2935 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Doi: "Transition Metals for Organic Synthesis."Wiley-VCH. 10 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Doi: "Palladium(0)-Catalyzed Domino Cyclization-Carbonylation of Alkenyl-Allenyl-Allylic Acetate."Bull. Chem. Soc. Jpn.. 71, ィイD1#ィエD112. 2929-2935 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Doi: "Palladium-catalyzed Cyalization of Allylic Acetates with Alkenes and Allenes, in 'Transition Metals for Organic Synthesis' Eds. M. Beller and C. Bolm."WILEY-VCH. Vol.2. 265-274 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Doi: "Palladium(0)-Catalyzed Domino Cyclization-Carbonylation of Alkenyl-Allenyl-Allylic Acetate."Bull.Chem.Soc.Jpn.. 71,^#12. 2929-2935 (1998)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Doi: "Transition Metals for Organic Synthesis."Wiley-VCH. 10 (1998)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Doi: "Palladium(0)-Catalyzed Cyclization of 6-(2-Alkenyl)-2,7-octadi-entl Acetates with Novel Distereofacial Selection." Synlett. ♯2. 145-146 (1996)

    • Related Report
      1998 Annual Research Report
  • [Publications] Y.Kawanami: "Rh(I)-Catalyzed Dehydrogenative Silylation of Divinylsilanes with Dimethylphenylsilane." Bull.Chem.Soc.Jpn.69 ♯12. 1117-1124 (1996)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Doi: "Novel Pd(0)-Catalyzed Intramolecular Reactions of Allylic Acetates with Allenic Moieties Followed by Tandem Cyclization." J.Org.Chem.61 ♯8. 2602-2603 (1996)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Doi: "Novel Pd(0)-Catalyzed Cyclization-Carbonylation of 2-Methyl-1-vinyl-5,6-heptadienyl Acetate:Total Synthesis of Iridomyrmecin." Chem.Lett.♯12. 1085-1086 (1996)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Doi: "Palladium(0)-Catalyzed Domino Cyclization-Carbonylation of Alkenyl-Allenyl-Allylic Acetate." Bull.Chem.Soc.Jpn.71 ♯12. 2929-2935 (1998)

    • Related Report
      1998 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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