Unknown

Dataset Information

0

Bond-weakening catalysis: conjugate aminations enabled by the soft homolysis of strong N-H bonds.


ABSTRACT: The ability of redox-active metal centers to weaken the bonds in associated ligands is well precedented, but has rarely been utilized as a mechanism of substrate activation in catalysis. Here we describe a catalytic bond-weakening protocol for conjugate amination wherein the strong N-H bonds in N-aryl amides (N-H bond dissociation free energies ?100 kcal/mol) are destabilized by ?33 kcal/mol upon by coordination to a reducing titanocene complex, enabling their abstraction by the weak H-atom acceptor TEMPO through a proton-coupled electron transfer process. Significantly, this soft homolysis mechanism provides a method to generate closed-shell, metalated nucleophiles under neutral conditions in the absence of a Brønsted base.

SUBMITTER: Tarantino KT 

PROVIDER: S-EPMC4657442 | biostudies-literature | 2015 May

REPOSITORIES: biostudies-literature

altmetric image

Publications

Bond-weakening catalysis: conjugate aminations enabled by the soft homolysis of strong N-H bonds.

Tarantino Kyle T KT   Miller David C DC   Callon Ted A TA   Knowles Robert R RR  

Journal of the American Chemical Society 20150513 20


The ability of redox-active metal centers to weaken the bonds in associated ligands is well precedented, but has rarely been utilized as a mechanism of substrate activation in catalysis. Here we describe a catalytic bond-weakening protocol for conjugate amination wherein the strong N-H bonds in N-aryl amides (N-H bond dissociation free energies ∼100 kcal/mol) are destabilized by ∼33 kcal/mol upon by coordination to a reducing titanocene complex, enabling their abstraction by the weak H-atom acce  ...[more]

Similar Datasets

| S-EPMC9671280 | biostudies-literature
| S-EPMC9303940 | biostudies-literature
| S-EPMC9931054 | biostudies-literature
| S-EPMC5266430 | biostudies-literature
| S-EPMC10141608 | biostudies-literature
| S-EPMC4807873 | biostudies-literature
| S-EPMC9906790 | biostudies-literature
| S-EPMC9383717 | biostudies-literature
| S-EPMC5110324 | biostudies-literature
| S-EPMC6440757 | biostudies-literature