biostudies-literatureRacys DTUniversity of BristolScience and Technology Facilities CouncilAstraZenecaEngineering and Physical Sciences Research Council5793-5801https://www.ebi.ac.uk/biostudies/studies/S-EPMC5520773biostudies-literatureUnknown6(10)Under optimised conditions, the Trost modular ligand (TML) series induces high levels of asymmetric induction in an extraordinarily wide range of reactions involving palladium π-allyl intermediates. Prior mechanistic investigations into reactions involving Pd-η3-C6H9 intermediates have focussed on the monomeric 13-membered ring formed via P,P-chelation of the ligand to Pd. However, it is also recognised that ring-opening oligomerisation provides a pool of high nuclearity Pd-η3-C6H9 species that, by affording a low level, or even the opposite sense, of asymmetric induction relative to the mononuclear species, are responsible for a reduction in selectivity under non-optimised conditions. Herein we dChemical sciencePd- η3 -C6H9 complexes of the Trost modular ligand: high nuclearity columnar aggregation controlled by concentration, solvent and counterion.PMC5520773EP/G036764/1Norrby POGrillo ILloyd-Jones GCRogers SERacys DTEastoe JfalsePd- η3 -C6H9 complexes of the Trost modular ligand: high nuclearity columnar aggregation controlled by concentration, solvent and counterion.Under optimised conditions, the Trost modular ligand (TML) series induces high levels of asymmetric induction in an extraordinarily wide range of reactions involving palladium π-allyl intermediates. Prior mechanistic investigations into reactions involving Pd-η3-C6H9 intermediates have focussed on the monomeric 13-membered ring formed via P,P-chelation of the ligand to Pd. However, it is also recognised that ring-opening oligomerisation provides a pool of high nuclearity Pd-η3-C6H9 species that, by affording a low level, or even the opposite sense, of asymmetric induction relative to the mononuclear species, are responsible for a reduction in selectivity under non-optimised conditions. Herein we d2015-01-01T00:00:00Z2015 Oct2025-04-05T21:12:15.893Z2019-03-27T02:51:11ZS-EPMC55207732879108710.1039/c5sc01181g