title: Catalytic asymmetric carbon-carbon bond formation via allylic alkylations with organolithium compounds.
abstract: Carbon-carbon bond formation is the basis for the biogenesis of nature's essential molecules. Consequently, it lies at the heart of the chemical sciences. Chiral catalysts have been developed for asymmetric C-C bond formation to yield single enantiomers from several organometallic reagents. Remarkably, for extremely reactive organolithium compounds, which are among the most broadly used reagents in chemical synthesis, a general catalytic methodology for enantioselective C-C formation has proven elusive, until now. Here, we report a copper-based chiral catalytic system that allows carbon-carbon bond formation via allylic alkylation with alkyllithium reagents, with extremely high enantioselectivities and able to tolerate several functional groups. We have found that both the solvent used and the structure of the active chiral catalyst are the most critical factors in achieving successful asymmetric catalysis with alkyllithium reagents. The active form of the chiral catalyst has been identified through spectroscopic studies as a diphosphine copper monoalkyl species.
authors.affiliation: Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
authors.forename: Manuel
authors.initials: M
authors.lastname: Pérez
authors.forename: Martín
authors.initials: M
authors.lastname: Fañanás-Mastral
authors.forename: Pieter H
authors.initials: PH
authors.lastname: Bos
authors.forename: Alena
authors.initials: A
authors.lastname: Rudolph
authors.forename: Syuzanna R
authors.initials: SR
authors.lastname: Harutyunyan
authors.forename: Ben L
authors.initials: BL
authors.lastname: Feringa
mesh_terms: D000478:Alkylation; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D018020:Lithium Compounds / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D018020:Lithium Compounds; D009942:Organometallic Compounds; D002244:Carbon