Mechanism of the Molybdenum-Mediated Cadogan Reaction. Castiñeira Reis, M., Marín-Luna, M., Silva López, C., & Faza, O. ACS Omega, 3(6):7019-7026, 2018.
doi  abstract   bibtex   
Oxygen atom transfer reactions are receiving increasing attention because they bring about paramount transformations in the current biomass processing industry. Significant efforts have therefore been made lately in the development of efficient and scalable methods to deoxygenate organic compounds. One recent alternative involves the modification of the Cadogan reaction in which a Mo(VI) core catalyzes the reduction of o-nitrostyrene derivatives to indoles in the presence of PPh3. We have used density functional theory calculations to perform a comprehensive mechanistic study on this transformation, in which we find two clearly defined stages: an associative path from the nitro to the nitroso compound, characterized by the reduction of the catalyst in the first step, and a peculiar mechanism involving oxazaphosphiridine and nitrene intermediates leading to an indole product, where the metal catalyst does not participate. © Copyright 2018 American Chemical Society.
@ARTICLE{CastineiraReis20187019,
author={Castiñeira Reis, M. and Marín-Luna, M. and Silva López, C. and Faza, O.N.},
title={Mechanism of the Molybdenum-Mediated Cadogan Reaction},
journal={ACS Omega},
year={2018},
volume={3},
number={6},
pages={7019-7026},
doi={10.1021/acsomega.8b01278},
abstract={Oxygen atom transfer reactions are receiving increasing attention because they bring about paramount transformations in the current biomass processing industry. Significant efforts have therefore been made lately in the development of efficient and scalable methods to deoxygenate organic compounds. One recent alternative involves the modification of the Cadogan reaction in which a Mo(VI) core catalyzes the reduction of o-nitrostyrene derivatives to indoles in the presence of PPh3. We have used density functional theory calculations to perform a comprehensive mechanistic study on this transformation, in which we find two clearly defined stages: an associative path from the nitro to the nitroso compound, characterized by the reduction of the catalyst in the first step, and a peculiar mechanism involving oxazaphosphiridine and nitrene intermediates leading to an indole product, where the metal catalyst does not participate. © Copyright 2018 American Chemical Society.},
}

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