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Cyclic (Alkyl)(amino)carbene Ligand-Promoted Nitro Deoxygenative Hydroboration with Chromium Catalysis: Scope, Mechanism, and Applications
- Source :
- Journal of the American Chemical Society. 143:1618-1629
- Publication Year :
- 2021
- Publisher :
- American Chemical Society (ACS), 2021.
-
Abstract
- Transition metal catalysis that utilizes N-heterocyclic carbenes as noninnocent ligands in promoting transformations has not been well studied. We report here a cyclic (alkyl)(amino)carbene (CAAC) ligand-promoted nitro deoxygenative hydroboration with cost-effective chromium catalysis. Using 1 mol % of CAAC-Cr precatalyst, the addition of HBpin to nitro scaffolds leads to deoxygenation, allowing for the retention of various reducible functionalities and the compatibility of sensitive groups toward hydroboration, thereby providing a mild, chemoselective, and facile strategy to form anilines, as well as heteroaryl and aliphatic amine derivatives, with broad scope and particularly high turnover numbers (up to 1.8 × 106). Mechanistic studies, based on theoretical calculations, indicate that the CAAC ligand plays an important role in promoting polarity reversal of hydride of HBpin; it serves as an H-shuttle to facilitate deoxygenative hydroboration. The preparation of several commercially available pharmaceuticals by means of this strategy highlights its potential application in medicinal chemistry.
- Subjects :
- chemistry.chemical_classification
Ligand
Hydride
General Chemistry
010402 general chemistry
01 natural sciences
Biochemistry
Combinatorial chemistry
Catalysis
0104 chemical sciences
chemistry.chemical_compound
Hydroboration
Colloid and Surface Chemistry
chemistry
Nitro
Carbene
Deoxygenation
Alkyl
Subjects
Details
- ISSN :
- 15205126 and 00027863
- Volume :
- 143
- Database :
- OpenAIRE
- Journal :
- Journal of the American Chemical Society
- Accession number :
- edsair.doi.dedup.....68ea8d0f05ccde464dab3a0ce6d32c1b
- Full Text :
- https://doi.org/10.1021/jacs.0c12318