Catalytic Asymmetric Synthesis of P-Stereogenic Phosphines: Beyond Precious Metals

In memory of Malcolm Green, with thanks for his enthusiasm and creativity

Abstract

Metal-catalyzed asymmetric synthesis of P-stereogenic phosphines is a potentially useful approach to a class of chiral ligands with valuable applications in asymmetric catalysis. We introduced this idea with chiral platinum and palladium catalysts, exploiting rapid pyramidal inversion in diastereomeric metal–phosphido complexes (ML*(PRR′)) to control phosphorus stereochemistry. This Account summarizes our attempts to develop related synthetic methods using earth-abundant metals, especially copper, in which weaker metal–ligand bonds and faster substitution processes were expected to result in more active catalysts. Indeed, precious metals were not required. Without any transition metals at all, we exploited related P-epimerization processes to prepare enantiomerically pure phosphiranes and secondary phosphine oxides (SPOs) from commercially available chiral epoxides.

1 Introduction

2 Copper-Catalyzed Phosphine Alkylation

3 Copper-Catalyzed Tandem Phosphine Alkylation/Arylation

4 Nickel-Catalyzed Phosphine Alkylation

5 Proton-Mediated P-Epimerization in Synthesis of Chiral Phosphiranes

6 Diastereoselective Synthesis of P-Stereogenic Secondary Phosphine Oxides (SPOs) from (+)-Limonene Oxide

7 Conclusions

Key words

P-stereogenic - inversion - chiral phosphine - phosphido - copper

Publication History

Received: 14 August 2020

Accepted after revision: 02 September 2020

Article published online:
13 October 2020

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