Synlett 2002(12): 1954-1965
DOI: 10.1055/s-2002-35576
ACCOUNT
© Georg Thieme Verlag Stuttgart · New York

Iridium Complex-Catalyzed Highly Selective Organic Synthesis

Ryo Takeuchi*
Department of Chemistry, Graduate School of Integrated Science, Yokohama City University, 22-2 Seto, Kanazawa-ku, Yokohama 236-0027, Japan
Fax: +81(45)7872218; e-Mail: rtakeuch@yokohama-cu.ac.jp;
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Publikationsverlauf

Received 30 January 2002
Publikationsdatum:
20. November 2002 (online)

Abstract

Two different synthetic reactions catalyzed by an iridium complex are discussed. The first is allylic alkylation and allylic amination. This reaction proceeds via a π-allyl iridium intermediate. The selectivity strongly depends on the structure of the allylic esters. Highly branched product-selective allylic substitution and highly Z-selective allylic substitution were achieved. The selectivities of allylic substitution described here have not been achieved in previous studies with other transition metal complexes. The second reaction is [2+2+2] cycloaddition of α,ω-diynes with monoynes. This reaction proceeds via iridacyclopentadiene and tolerates various functional groups. Functionalized monoynes can be used. These results show that an iridium complex can be a useful catalyst for carbon-carbon and carbon-heteroatom bond formation.

  • 1 Introduction

  • 2 Allylic Alkylation

  • 2.1 Branched Product-Selective Allylic Alkylation

  • 2.2 Z-Selective Allylic Alkylation

  • 3 Allylic Amination

  • 3.1 Branched Amine-Selective Allylic Amination

  • 3.2 Z-Selective Allylic Amination

  • 4 [2+2+2] Cycloaddition of α,ω-Diynes with Monoynes

  • 5 Conclusion