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Synlett 2008(12): 1747-1758  
DOI: 10.1055/s-2008-1077903
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Optically Active Chiral Ligands, Ferrocenyloxazolinylphosphines (FOXAPs): Development and Application to Catalytic Asymmetric Reactions

Yoshihiro Miyakea, Yoshiaki Nishibayashi*a, Sakae Uemurab
a Institute of Engineering Innovation, School of Engineering, University of Tokyo, Yayoi, Bunkyo-ku, Tokyo 113-8656, Japan
e-Mail: ynishiba@sogo.t.u-tokyo.ac.jp;
b Faculty of Engineering, Okayama University of Science, Ridai-cho, Okayama 700-0005, Japan
Further Information

Publication History

Received 26 February 2008
Publication Date:
03 July 2008 (online)

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Abstract

The development of optically active chiral ligands, ferrocenyloxazolinylphosphines (FOXAPs), and their application to catalytic asymmetric reactions are reviewed. FOXAPs have been prepared in high yields from the corresponding chiral oxazolinylferrocenes via diastereoselective lithiation followed by quenching with chlorodiphenylphosphine. They work quite effectively as chiral ligands for a variety of transition-metal-catalyzed asymmetric reactions such as hydrosilylation and transfer hydrogenation of ketones and imines, kinetic resolution of alcohols, carbon-carbon bond-forming reactions and ring-opening reactions.

 1 Introduction

 2 Preparation of Optically Active Ferrocenyloxazolinylphosphines (FOXAPs)

 3 Rhodium- and Iridium-Catalyzed Asymmetric Hydrosilylation of Ketones and Imines

 3.1 Rhodium- and Iridium-Catalyzed Asymmetric Hydrosilylation of Ketones

 3.2 Rhodium- and Iridium-Catalyzed Asymmetric Hydrosilylation of Imines

 4 Ruthenium-Catalyzed Asymmetric Hydrosilylation of Ketones, Imines and Oximes

 4.1 Ruthenium-Catalyzed Asymmetric Hydrosilylation of Ketones and Imines

 4.2 Ruthenium-Catalyzed Asymmetric Hydrosilylation of Oximes

 5 Ruthenium-Catalyzed Enantioselective Redox Reactions of Ketones and Alcohols, and Application to Sequential Reactions

 5.1 Ruthenium-Catalyzed Asymmetric Transfer Hydrogenation of Ketones and Oxidative Kinetic Resolution of Secondary Alcohols

 5.2 Ruthenium-Catalyzed Enantioselective Hydrogenation of Ketones

 5.3 Application of Enantioselective Redox Reactions to Sequential Reactions

 6 Kinetic Resolution of Secondary Alcohols via Palladium-Catalyzed Benzoylation Using Carbon Monoxide and Organobismuth Compounds

 7 Palladium-Catalyzed Asymmetric Allylic Substitution Reactions

 8 Nickel-Catalyzed Asymmetric Allylic Substitution Reactions

 9 Miscellaneous Reactions

10 Conclusion

Key words

asymmetric reactions - chiral ligands - ferrocenes - ­oxazolines - phosphines

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11

The optically active ferrocenyloxazolinylphosphine 1c bearing an i-Pr group at the 4-position of the oxazoline ring is commercially available from Wako Pure Chemical Industries (Japan) as ip-FOXAP (ferrocenyloxazolinyl-phosphine) (065-04331).

15

Nishibayashi Y., Uemura S. unpublished results.

19

The ruthenium(II) complex 3b bearing optically active ferrocenyloxazolinylphosphine 1c is commercially available from Strem in collaboration with Solvias (44-0443).