Issue 28, 2013

Meta-analysis in asymmetric catalysis. Influence of chelate geometry on the roles of PN chelating ligands

Abstract

All X-ray structures of PN ligands forming 6-ring metal complex chelates have been retrieved from the CDS database, and those lacking chelate chirality filtered out. Many of the remainder fit naturally into four main families (PPFA, FcPhox, Phox and Quinap), which have been widely applied to asymmetric catalysis in diverse ways. It is known through experimental observation that certain of these ligand structures are more effective for specific classes of reaction but there has been little by way of explanation for their divergent behaviour. In this paper we examine the wide variation of conformations within individual families of PN complexes in the solid state, establish common features, and make cross-correlations with their effectiveness in specific catalytic asymmetric reactions. The extent of rigidity in the chelate varies widely and yet flexible complexes may be extremely effective in asymmetric catalysis. These observations emphasise the importance of induced fit between reactants and catalyst and militate against over-reliance on rigid lock-and-key models.

Graphical abstract: Meta-analysis in asymmetric catalysis. Influence of chelate geometry on the roles of PN chelating ligands

Article information

Article type
Paper
Submitted
18 ก.พ. 2556
Accepted
12 เม.ย. 2556
First published
16 เม.ย. 2556

Org. Biomol. Chem., 2013,11, 4591-4601

Meta-analysis in asymmetric catalysis. Influence of chelate geometry on the roles of PN chelating ligands

M. P. Carroll, P. J. Guiry and J. M. Brown, Org. Biomol. Chem., 2013, 11, 4591 DOI: 10.1039/C3OB40360B

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements