title: Robust and Porous β-Diketiminate-Functionalized Metal-Organic Frameworks for Earth-Abundant-Metal-Catalyzed C-H Amination and Hydrogenation.
abstract: We have designed a strategy for postsynthesis installation of the β-diketiminate (NacNac) functionality in a metal-organic framework (MOF) of UiO-topology. Metalation of the NacNac-MOF (I) with earth-abundant metal salts afforded the desired MOF-supported NacNac-M complexes (M = Fe, Cu, and Co) with coordination environments established by detailed EXAFS studies. The NacNac-Fe-MOF catalyst, I•Fe(Me), efficiently catalyzed the challenging intramolecular sp(3) C-H amination of a series of alkyl azides to afford α-substituted pyrrolidines. The NacNac-Cu-MOF catalyst, I•Cu(THF), was effective in promoting the intermolecular sp(3) C-H amination of cyclohexene using unprotected anilines to provide access to secondary amines in excellent selectivity. Finally, the NacNac-Co-MOF catalyst, I•Co(H), was used to catalyze alkene hydrogenation with turnover numbers (TONs) as high as 700,000. All of the NacNac-M-MOF catalysts were more effective than their analogous homogeneous catalysts and could be recycled and reused without a noticeable decrease in yield. The NacNac-MOFs thus provide a novel platform for engineering recyclable earth-abundant-element-based single-site solid catalysts for many important organic transformations.
authors.affiliation: Department of Chemistry, University of Chicago , 929 East 57th Street, Chicago, Illinois 60637, United States.
authors.forename: Nathan C
authors.initials: NC
authors.lastname: Thacker
authors.affiliation: Department of Chemistry, University of Chicago , 929 East 57th Street, Chicago, Illinois 60637, United States.
authors.forename: Zekai
authors.initials: Z
authors.lastname: Lin
authors.affiliation: Department of Chemistry, University of Chicago , 929 East 57th Street, Chicago, Illinois 60637, United States.
authors.forename: Teng
authors.initials: T
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, University of Chicago , 929 East 57th Street, Chicago, Illinois 60637, United States.
authors.forename: James C
authors.initials: JC
authors.lastname: Gilhula
authors.affiliation: Department of Chemistry, University of Chicago , 929 East 57th Street, Chicago, Illinois 60637, United States.
authors.forename: Carter W
authors.initials: CW
authors.lastname: Abney
authors.affiliation: Department of Chemistry, University of Chicago , 929 East 57th Street, Chicago, Illinois 60637, United States.
authors.forename: Wenbin
authors.initials: W
authors.lastname: Lin