Iridium Complex-Catalyzed Highly Selective Organic Synthesis

Ryo  Takeuchi

doi:10.1055/s-2002-35576

ACCOUNT

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;

Abstract

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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

Key words

iridium complex - catalysis - π-allyl iridium - iridacyclopentadiene - allylic esters - alkynes

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