A Metal–Organic Framework with Exceptional Activity for C−H Bond Amination

Abstract

The development of catalysts capable of fast, robust C-H bond amination under mild conditions is an unrealized goal despite substantial progress in the field of C-H activation in recent years. A Mn-based metal-organic framework (CPF-5) is described that promotes the direct amination of C-H bonds with exceptional activity. CPF-5 is capable of functionalizing C-H bonds in an intermolecular fashion with unrivaled catalytic stability producing >10 turnovers.

Radical‐Type Reactivity and Catalysis by Single‐Electron Transfer to or from Redox‐Active Ligands

“…disclosed a well‐defined, crystallographically characterized, paramagnetic high‐spin ( S= 2) Fe III (Cl) 2 ( L1 ISQ ) complex Q for the intramolecular C(sp 3 )−H amination of a broad range of organoazides, with TONs of up to 620 at 0.1 mol % catalyst loading (Scheme ) . This system is at least one order of magnitude more active than all other reported systems to date, all of which operate through metalloradical catalysis . The Fe III ‐complex could be quantitatively recycled and re‐used after catalysis.…”

“…[47] This system is at least one order of magnitude morea ctive than all other reporteds ystems to date, all of which operate through metalloradicalc atalysis. [48][49][50][51] The Fe III -complex could be quantitatively recycled and re-used after catalysis. It was established that in situ reduction under the same conditions as for the Pd-system led to Fe-centered rather than ligand-centered reduction, with subsequent disproportionation to afford ac rystallographically characterized homoleptic Fe II (L1 ISQ ) 2 complex that was completely inactive for the CÀHa mination reaction.…”

Uncatalyzed Oxidative C−H Amination of 9,10‐Dihydro‐9‐Heteroanthracenes: A Mechanistic Study

“…[2][3][4][5] Keyd evelopmentsa re theu se of activated [6][7][8] andn on-activated organic azides, [9][10][11][12][13][14][15] Haloamine-T [16,17] and( in situ generated) iminoiodanes( PhI = NR)a sn itrene precursors (Figure1). [18][19][20][21][22][23] Transitionmetalc omplexes have proven to be excellentc atalysts fort hese aminationr eactions,a nd thec ommonlya cceptedm echanism comprisest he formationo fareactive metal-nitrenei ntermediate, followed by stepwise hydrogen atom abstractiona nd radicalr ecombination or concertedi nsertion of then itrene into the CÀHb ond. [3,5,24] In addition,o rganocatalysts that area lsoc apableo fnitrene transfer have been reported.…”

A Tale of Two Trimers from Two Different Worlds: A COF‐Inspired Synthetic Strategy for Pore‐Space Partitioning of MOFs

“…Metal-organic frameworks (MOFs) are crystalline porous materials with intriguing structural characteristics [1] and have attracted intense attention in the last two decades for various applications,s uch as gas sorption, [2] separation, [3] and catalysis. [4] Pore-space partitioning has been shown to be aversatile design strategy for constructing crystalline porous materials (CPMs) with much enhanced chemical stability and gassorption properties. [5] Ap rominent platform involves the introduction of C 3 -symmetric pore-partitioning agents into hexagonal channels of MIL-88/MOF-235-type structures, [6] also known as the acs net, to form 9-connected pacs frameworks.…”