期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 137, 期 20, 页码 6440-6443出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b03428
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资金
- Princeton University
- NIH [R01 GM113105]
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 similar to 100 kcal/mol) are destabilized by similar to 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 Bronsted base.
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