Amination of carboranes has a good application prospect in organic and pharmaceutical synthesis. However, the current methods used for this transformation suffer from limitations. Herein, we report a practical method for a highly regioselective formation of a B−N bond by Pd(II)-catalyzed B( 9)-H amination of oand m-carboranes in hexafluoroisopropanol (HFIP) with different nitrogen sources under air atmosphere. The silver salt and HFIP solvent play critical roles in the present protocol. The mechanistic study reveals that the silver salt acts as a Lewis acid to promote the electrophilic palladation step by forming a heterobimetallic active catalyst PdAg(OAc) 3 ; the strong hydrogen-bond-donating ability and low nucleophilicity of HFIP enhance the electrophilic ability of Pd(II). It is believed that these N-containing carboranes are potentially of great importance in the synthesis of new pharmaceuticals.
Herein,
we report a metal-free radical tandem C–H amination
and bromination reaction with dibromohydantoin (DBH) as both the amination
and bromination reagents and water as the main solvent. The reaction
involves in intramolecular C–H amination and electrophilic
bromination using cheap commercially available DBH. The products represent
heterocyclic building blocks, readily modifiable by classical cross-coupling
reactions.
Despite the great importance of nitrogen-containing carboranes in organic and pharmaceutical synthesis, current methods to generate them are very limited and usually rely on the use of expensive transition metals....
Herein, we report a metal-free and step-economic synthesis of phenanthridines from 2-biarylmethanamines under mild conditions. The reaction involves iodine-supported intramolecular C−H amination and oxidation of 5,6-dihydrophenanthridine under air and benign visible light. The mechanism study reveals that visible light plays a key role in both these steps.
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