Coordination of the Trost Modular Ligand to Palladium Allyl Fragments: Oligomers, Monomers, and Memory Effects in Catalysis

Abstract

Organic chemistryOrganic chemistry Z 0200 Coordination of the Trost Modular Ligand to Palladium Allyl Fragments: Oligomers, Monomers, and Memory Effects in Catalysis-[42 refs.]. -(LLOYD-JONES, G. C.; STEPHEN, S. C.; FAIRLAMB, I. J. S.; MARTORELL, A.; DOMINGUEZ, B.; TOMLIN, P. M.; MURRAY, M.; FERNANDEZ, J. M.; JEFFERY, J. C.; RIIS-JOHANNESSEN, T.; et al.; Pure Appl. Chem. 76 (2004) 3, 589-601; Sch. Chem., Univ. Bristol, Cantock's Close, Bristol BS8 1TS, UK; Eng.) -Lindner 39-253

2H-quadrupolar coupling-based analysis of stereochemical and regiochemical memory in the Pd-catalysed allylic alkylation of iso-cinnamyl type substrates employing the chiral monophosphine ligands ‘MOP’ and ‘MAP’

“…With ligand 1, a number of factors have been identified as potential contributors to the net memory effect. These include intimate ionpairing [6a], ionic strength [10], P ,O -chelation [6e], PdÁ/ allyl-oligomerisation [6i] and conformational loss of chelated ligand C 2 -symmetry [10]. However, the origins of the memory effect with MOP and MAP are less complex [6g] and we have introduced a simple stereochemical convergence ('sc') term by which the effects are readily quantified through the deployment of a 2 H label at the stereogenic centre of the substrate [11].…”