Chiral 1‐Phosphabarrelene‐Pyridines as Suitable Ligands for the Rh/Ir‐Catalyzed Asymmetric Hydrogenation of Olefins

Author:

Saltó Joan1,Tarr Daniel1,Petrov Andrey2,Reich Dorian2,Weber Manuela2,Biosca Maria1ORCID,Pàmies Oscar1,Müller Christian2,Diéguez Montserrat1ORCID

Affiliation:

1. Universitat Rovira i Virgili Departament de Química Física i Inorgànica, C/ Marcel ⋅ lí Domingo, 1 43007 Tarragona Spain

2. Institut für Chemie und Biochemie Freie Universität Berlin Fabeckstrasse 34/36 14195 Berlin Germany

Abstract

AbstractHerein, we report the synthesis of chiral phosphabarrelene‐pyridine ligands. Their synthesis benefit from modified reaction conditions to overcome the low yields normally associated with the [4+2] cycloaddition reaction of phosphinines with hexafluoro‐2‐butyne, which is a key to install the P‐stereocenter in the phosphabarrelene. Their potential as chelating ligands in asymmetric catalysis was assessed in the Rh‐ and Ir‐catalyzed hydrogenation of cyclic β‐enamides and β‐dehydroamino acid derivatives. The catalytic system containing a tert‐butyl substituent at the ortho position of the phosphabarrelene moiety successfully hydrogenates a range of cyclic β‐enamides (ee's between 92% to 94%) and β‐dehydroamino acid derivatives (ee's between 93% to 95%). Moreover, the reactions can be carried out in the environmentally friendly 1,2‐propylene carbonate as solvent with no loss of enantioselectivity. Mechanistic studies with the Rh/P,N catalytic systems agree with the Landis‐Halpern mechanism and explain the influence of the substituent at the phosphabarrelene on enantioselectivity. Finally, the hydrogenation reactions can be carried out at large scale maintaining high enantioselectivities.

Publisher

Wiley

Subject

General Chemistry

Reference101 articles.

1. For books on asymmetric catalysis see for example:

2. Comprehensive Asymmetric Catalysis I–III

3. Catalytic Asymmetric Synthesis

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