• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to project page

1998 Fiscal Year Final Research Report Summary

Umpolung of pi-Allylpalladium with Diethylzinc and Synthetic Application

Research Project

Project/Area Number 08455431
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionFaculty of Engineering, Nagasaki University

Principal Investigator

TAMURA Yoshinao  Nagasaki University, Faculty of Engineering, Professor of Chem., 工学部, 教授 (80026319)

Co-Investigator(Kenkyū-buntansha) KIMURA Masanari  Nagasaki University, Faculty of Engineering, Assistant Professor, 工学部, 助手 (10274622)
Project Period (FY) 1996 – 1998
Keywordsp-Allylpalladium / Umpolung / Diethylzine / Allylation / beta-Decarbopalladation / omega-Dienyl Aldehydes
Research Abstract

pi-Allylpalladium is usually recognized to serve as synthetically important electrophilic allylating agent toward many nucleophiles (organometals). This research mechanistically clarified that pi-allylpalladium complexes, catalytically generated in situ by the reaction of allylic esters and Pd(O), undergo the alkyl ligand exchange with diethylzinc and provide a mixture of allylzinc and diethylpalladium species. The thus formed allylzinc demonstrated unique regio-and stereoselectivity for the reaction with carbonyl compounds. For example, 1,3-disubstituted allylzinc reacted with aldehyde to provide (Z)-anti-homoallyl alcohols with high stereoselectivity. Furthermore, the present methodology turned out to be very useful and powerful to generate stereochemically defined allylzinc species, the species being very difficult to generate by other methods. The similar umpolung reaction proceeds between pi-allylpalladium and triethylborane (unpublished results).
In the related research, it was demonstrated that pi-allylpalladium serves as an active species to promote beta-decarbopalladation reaction. This reaction also proceeds catalytically with respect to palladium and furnishes omega-dienyl aldehydes and ketones in good yields. Chemical & Engineering News picked up this report from the following points of view ; the uniqueness of the reaction type and the synthetic importance of the products as synthetic intermediates.

  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] M.Shimizu: "Unique Regio-and Stereoselectivity in the Allylation of Benzaidehyde with 2-Substituted Allylzincs Generated by Umpolung of π-Allyipalladium" Tetrahedron Lett.39. 609-612 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Kimura: "Novel and Highly Regio-and Stereoselective Nickel-Catalyzed Homoallylation of Benzaldehyde with 1,3-Dienes" J.Am.Chem.Soc. 120. 4033-4034 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Kimura: "Novel Carbonyl-Dependent Regioselective Allylation via Diethylzinc-Mediated Umpolung of π-Allylpalladium" Tetrahedron Lett. 39. 6903-6906 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Horino: "Efficient Entry to Tetrahydropyridines:Addition of Enol Ethers to Allene Sulfonamides Involving a Novel 1,3-Sulfonyl Shift" Angew.Chem.(in press).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Kimura: "Nickel-Catalyzed Homoallylation of Aldehydes and Ketones with 1,3-Dienes Promoted Complementarily by Diethylzinc and Triethylborane" Angew.Chem.(in press).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Harayama: "Selective Reaction of π-Allyl(alkyloxy)palladium(II)Complexes toward β-Decarbopalladation,β-Dehydropalladation,and Reductive Elimination" Tetrahedren Lett.39. 8475-8478 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Shimizu, M.Kimura, S.Tanaka, Y.Tamaru: "Unique Regio- and Stereoselectivity in the Allylation of Benzaldehyde with 2-Substituted Allylzincs Generated by Umpolung of pi-Allylpalladium" Tetrahedron Lett.39. 609-612 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Kimura, A.Ezoe, K.Shibata, Y.Tamaru: "Novel and Highly Regio- and Stereoselective Nickel-Catalyzed Homoallylation of Benzaldehyde with 1,3-Dienes" J.Am.Chem.Soc.120. 4033-4034 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Kimura, Y.Ogawa, M.Shimizu, M.Sueishi, S.Tanaka, Y.Tamaru: "Novel Carbonyl-Dependent Regioselective Allylation via Diethylzinc-Mediated Umpolung of pi-Allylpalladium" Tetrahedron Lett.39. 6903-6906 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Harayama, M.Kimura, S.Tanaka, Y.Tamaru: "Selective Reaction of pi-Allyl (alkyloxy) palladium (II) Complexes toward beta-Decarbopalladation, b-Dehydropalladation, and Reductive Elimination" Tetrahedron Lett.39. 8475-8478 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Horino, M.Kimura, Y.Wakamiya, T.Okajima, Y.Tamaru: "Efficient Entry to Tstrahydropyridines : Addition of Enol Ethers to Allene Sulfonnamides Involving a Novel 1,3-Sulfonyl Shift" Angew.Chem.Int.Ed.Eng.38 (IN PRESS). (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Kimura, H.Fujimatsu, A.Ezoe, K.Shibata, M.Shimizu, S.Matsumoto, Y.Tamaru: "Nickel-Catalyzed Homoallylation of Aldehydes and Ketones with 1,3-Dienes Promoted Complementarily by Diethylzinc and Triethylborane" Angew.Chem.Int.Ed.Eng.38 (IN PRESS). (1999)

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

URL: 

Published: 1999-12-08  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi