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Review

Enantiomerically Pure ansa-η5-Complexes of Transition Metals as an Effective Tool for Chirality Transfer

by
Pavel V. Kovyazin
,
Leonard M. Khalilov
and
Lyudmila V. Parfenova
*
Institute of Petrochemistry and Catalysis, Ufa Federal Research Center, Russian Academy of Sciences, 141 Prospekt Oktyabrya, 450075 Ufa, Russia
*
Author to whom correspondence should be addressed.
Molecules 2025, 30(12), 2511; https://doi.org/10.3390/molecules30122511 (registering DOI)
Submission received: 28 April 2025 / Revised: 2 June 2025 / Accepted: 4 June 2025 / Published: 8 June 2025
(This article belongs to the Special Issue Advances in Metallocene Chemistry)

Abstract

Chiral ansa-η5-complexes of transition metals have shown remarkable efficacy in organometallic synthesis and catalysis. Additionally, enantiomerically pure ansa-complexes hold promise for the development of novel chiral materials and pharmaceuticals. The discovery and synthesis of a diverse range of group IVB and IIIB metal complexes represents a significant milestone in the advancement of stereoselective catalytic methods for constructing metal-C, C-C, C-H, and C-heteroatom bonds. The synthesis of enantiomerically pure metallocenes can be accomplished through several strategies: utilizing optically active precursors of η5-ligands, separation of diastereomers of complexes with enantiomerically pure agents, and synthesis via the stereocontrolled reactions of enantiomerically pure σ-complexes with prochiral anions of η5-ligands. This review focuses on the analysis of various nuances of the synthesis of enantiomerically pure ansa-η5-complexes of titanium and lanthanum families. Their applicability as effective catalysts in asymmetric carbomagnesiation, carbo- and cycloalumination, oligo- and polymerization, Diels–Alder cycloaddition, reactions of zirconaaziridines, cyclization, hydrosilylation, hydrogenation, hydroamination, and other processes are highlighted as well.
Keywords: ansa-metallocenes; enantiomerically pure complexes; stereoselectivity; asymmetric synthesis; reaction mechanisms ansa-metallocenes; enantiomerically pure complexes; stereoselectivity; asymmetric synthesis; reaction mechanisms

Share and Cite

MDPI and ACS Style

Kovyazin, P.V.; Khalilov, L.M.; Parfenova, L.V. Enantiomerically Pure ansa-η5-Complexes of Transition Metals as an Effective Tool for Chirality Transfer. Molecules 2025, 30, 2511. https://doi.org/10.3390/molecules30122511

AMA Style

Kovyazin PV, Khalilov LM, Parfenova LV. Enantiomerically Pure ansa-η5-Complexes of Transition Metals as an Effective Tool for Chirality Transfer. Molecules. 2025; 30(12):2511. https://doi.org/10.3390/molecules30122511

Chicago/Turabian Style

Kovyazin, Pavel V., Leonard M. Khalilov, and Lyudmila V. Parfenova. 2025. "Enantiomerically Pure ansa-η5-Complexes of Transition Metals as an Effective Tool for Chirality Transfer" Molecules 30, no. 12: 2511. https://doi.org/10.3390/molecules30122511

APA Style

Kovyazin, P. V., Khalilov, L. M., & Parfenova, L. V. (2025). Enantiomerically Pure ansa-η5-Complexes of Transition Metals as an Effective Tool for Chirality Transfer. Molecules, 30(12), 2511. https://doi.org/10.3390/molecules30122511

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