C–N Bond Formation between Alcohols and Amines Using an Iron Cyclopentadienone Catalyst

Abstract

An iron-tetraphenylcyclopentadienone tricarbonyl complex is demonstrated to act as a precursor of a catalyst for the formation of C-N bonds through a "hydrogen-borrowing" reaction between amines and alcohols.

Divergent Coupling of Alcohols and Amines Catalyzed by Isoelectronic Hydride MnI and FeII PNP Pincer Complexes

“…Kempe and co‐workers described a new Co PNP pincer catalyst based on a triazine backbone, which was highly active for the alkylation of aromatic amines . The groups of Feringa and Barta, Wills, and Zhao reported the alkylation of amines with alcohols to give amines by utilizing Fe catalysts featuring functionalized cyclopentadienone or hydroxycyclopentadienyl ligands based upon Knölker's complex or derivatives thereof . We described the application of well‐defined Co II catalysts, which feature a PCP ligand based on the 1,3‐diaminobenzene scaffold .…”

Iron‐Catalyzed Allylic Amination Directly from Allylic Alcohols

“…Based on the experimental observations and relevant reports on the use of Knölker's complex for borrowing hydrogen methodology (redox process),, we proposed a possible mechanism for the Fe‐catalyzed allylic amination directly from alcohol (Scheme ). First, the de‐coordination of CO in the presence of Me 3 NO gives 16e − unsaturated complex B , which upon coordination with an alcohol leads to intermediate complex C —in which the alcohol was activated through the hydrogen bonding between the alcoholic hydrogen and cyclopentadienone.…”

A Step into an eco‐Compatible Future: Iron‐ and Cobalt‐catalyzed Borrowing Hydrogen Transformation

“…[9] Contemporaneously,t he group of Zhao, using iron cyclopentadienone complex cat5,s howedt hat addition of aL ewis acid co-catalyst such as AgF accelerated the imine formation, extending the scope of alcohola mination to the use of aw ide range of secondary alcohols (Scheme 3, bottom right). [9] Contemporaneously,t he group of Zhao, using iron cyclopentadienone complex cat5,s howedt hat addition of aL ewis acid co-catalyst such as AgF accelerated the imine formation, extending the scope of alcohola mination to the use of aw ide range of secondary alcohols (Scheme 3, bottom right).…”

“…Soon after,W ills and collaborators reportedt hat cat4 could also promotet his reactionw ith increased yields for secondary alcohola mination (Scheme 3, bottom center). [9] Contemporaneously,t he group of Zhao, using iron cyclopentadienone complex cat5,s howedt hat addition of aL ewis acid co-catalyst such as AgF accelerated the imine formation, extending the scope of alcohola mination to the use of aw ide range of secondary alcohols (Scheme 3, bottom right). [10] In this process, the use of cat5,amodified version of cat2 with an itrile ligand prompt to decoordination upon heating, avoided the use of Me 3 NO as additive.…”

“…ChemSusChem 2016, 9,[28][29][30] www.chemsuschem.org meta-aminoa niline could be alkylated using two structurally differenta lcohols, thus providing access to diversely functionalized unsymmetrical diamines.…”