Iron Chemistry Made Easy: Chiral N₂P₂ Ligands for Asymmetric Catalysis

Abstract

In this account, we summarize our recent work on the preparation of C ₂-symmetric macrocyclic N₂P₂ and open-chain NPPN iron(II) complexes. The investigation of these new ligand classes is enabled by the development of a synthetic route to the key enantiopure, P-stereogenic dialdehyde. Macrocyclization with a diamine affords N₂P₂ ligands, the iron(II) complexes of which are highly active and selective precatalysts for the asymmetric transfer hydrogenation of ketones. Condensation with monoamines affords open-chain NPPN ligands, of which the highly azaphilic iron(II) complexes are tested in the asymmetric Strecker reaction.

1 Introduction

1.1 Iron Complexes: The Issue of Stability

1.2 Open-Chain PNNP Ligands

1.3 Goals and Motivation

2 N₂P₂ Macrocycles

2.1 The Key C ₂-Symmetric Synthon

2.2 C ₂-Symmetric N₂P₂ Macrocycles

3 Macrocyclic Iron(II) Complexes

3.1 Bis(acetonitrile) N₂P₂ Complexes

3.2 Bis(acetonitrile) (NH)₂P₂ Complexes

3.3 Enlarging the Toolbox: Isonitrile (CNR) Ligands

3.4 Asymmetric Transfer Hydrogenation Fe/N₂P₂

4 Chiral Open-Chain NPPN Ligands

4.1 Synthesis of Bis(acetonitrile) Complexes

4.2 Complex Derivatization

4.3 Asymmetric Transfer Hydrogenation Fe/NPPN

4.4 Strecker Reaction of Azomethine Imines

5 Conclusion and Outlook

Key words

macrocycles - iron - asymmetric catalysis - hydrogen transfer - alcohols

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