title: Exchange Processes in Shibasaki's Rare Earth Alkali Metal BINOLate Frameworks and Their Relevance in Multifunctional Asymmetric Catalysis.
abstract: Shibasaki's rare earth alkali metal BINOLate (REMB) catalysts (REMB; RE = Sc, Y, La - Lu; M = Li, Na, K; B = 1,1-bi-2-naphtholate; RE/M/B = 1/3/3) are among the most successful enantioselective catalysts and have been employed in a broad range of mechanistically diverse reactions. Despite the phenomenal success of these catalysts, several fundamental questions central to their reactivity remain unresolved. Combined reactivity and spectroscopic studies were undertaken to probe the identity of the active catalyst(s) in Lewis-acid (LA) and Lewis-acid/Brønsted-base (LA/BB) catalyzed reactions. Exchange spectroscopy provided a method to obtain rates of ligand and alkali metal self-exchange in the RE/Li frameworks, demonstrating the utility of this technique for probing solution dynamics of REMB catalysts. Isolation of the first crystallographically characterized REMB complex with substrate bound enabled stoichiometric and catalytic reactivity studies, wherein we observed that substrate deprotonation by the catalyst framework was necessary to achieve selectivity. Our spectroscopic observations in LA/BB catalysis are inconsistent with previous mechanistic proposals, which considered only tris(BINOLate) species as active catalysts. These findings significantly expand our understanding of the catalyst structure in these privileged multifunctional frameworks and identify new directions for development of new catalysts.
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Jerome R
authors.initials: JR
authors.lastname: Robinson
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Jun
authors.initials: J
authors.lastname: Gu
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Carroll
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Eric J
authors.initials: EJ
authors.lastname: Schelter
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Walsh