title: Precise structure activity relationships in asymmetric catalysis using carbohydrate scaffolds to allow ready fine tuning: dialkylzinc-aldehyde additions.
abstract: The ready construction of 24 stereochemically and functionally diverse carbohydrate ligand structures from a core D-glucosamine scaffold has allowed the evaluation of broad ranging structure activity relationships in ligand accelerated zincate additions to aldehydes, with variations in deltadeltaG+/+(R-S) of up to 5650 J mol(-1) that create opposing senses of asymmetric induction and that are consistent with models based on several ligand X-ray structures and molecular mechanics analysis. Factorial analysis of enantioselectivity using key dihedral angles and steric volume on N-2 also highlight the potential for the use of factorial design in ligand construction.
authors.affiliation: Dyson Perrins Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, UK OX1 3QY.
authors.forename: Daniel P G
authors.initials: DP
authors.lastname: Emmerson
authors.forename: Renaud
authors.initials: R
authors.lastname: Villard
authors.forename: Claudia
authors.initials: C
authors.lastname: Mugnaini
authors.forename: Andrei
authors.initials: A
authors.lastname: Batsanov
authors.forename: Judith A K
authors.initials: JA
authors.lastname: Howard
authors.forename: William P
authors.initials: WP
authors.lastname: Hems
authors.forename: Robert P
authors.initials: RP
authors.lastname: Tooze
authors.forename: Benjamin G
authors.initials: BG
authors.lastname: Davis
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D002241:Carbohydrates / Q000737:chemistry*; D002384:Catalysis; D013329:Structure-Activity Relationship; D015032:Zinc / Q000737:chemistry*
chemical_list: D000447:Aldehydes; D002241:Carbohydrates; D015032:Zinc