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Synlett 2012(4): 509-523  
DOI: 10.1055/s-0031-1290315
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Synthetic Utility of Chiral Bis(oxazolinyl)phenyl Transition-Metal Complexes

Jun-ichi Ito, Hisao Nishiyama*
Department Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
Fax: +81(52)7893336; e-Mail: hnishi@apchem.nagoya-u.ac.jp;
Further Information

Publication History

Received 3 August 2011
Publication Date:
19 January 2012 (online)

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Abstract

Transition-metal complexes with a chiral bis(oxazolinyl)phenyl (Phebox) ligand can construct suitable chiral environments around metal centers. Thus far, a number of transition-metal complexes in the range of early to late metals have been prepared via transmetalation, cyclometalation, and oxidative addition. The fundamental properties and catalytic activities of the resulting Phebox complexes have been extensively investigated. In particular, the Phebox-Rh and Phebox-Ru complexes were found to serve as efficient and selective catalysts in asymmetric reactions for carbon-carbon bond formation, reduction of unsaturated bonds, and functionalization reactions. In this Account, we summarize details of the Phebox complexes in terms of preparations, coordination chemistry, and catalytic applications.

1 Introduction

2 Preparation of Phebox-Metal Complexes

3 Catalytic and Stoichiometric Reactions Mediated by Phebox-Rh Complexes

4 Ru- and Fe-Catalyzed Asymmetric Catalytic Reactions

5 Pt- and Pd-Catalyzed Asymmetric Catalytic Reactions

6 Conclusions

Key words

asymmetric catalysis - oxazoline - pincer complex - rhodium - ruthenium