Rh(III)-Catalyzed [5+2] Oxidative Annulation of Cyclic Arylguanidines and Alkynes to 1,3-Benzodiazepines. A Striking Mechanistic Proposal from DFT
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ISSN: 1523-7060
E-ISSN: 1523-7052
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American Chemical Society
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Abstract
A novel and mild Rh(III)-catalyzed [5+2] oxidative annulation between cyclic arylguanidines and alkynes efficiently affords 1,3-benzodiazepines (pentacyclic guanidines). The use of O2 as the sole oxidant in place commonly used metal oxidants such as AgOAc clearly improves the efficiency of the oxidative annulation process. The mechanism of the cycloaddition most likely involves the formation of an eight-membered rhodacycle. DFT calculations support a striking mechanistic proposal for the [5+2] oxidative annulation.
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NOTICE: This is the peer reviewed version of the following article: Martínez-Yáñez, N., Suárez, J., Cajaraville, A., Varela, J. A., Saá, C. (2019). Rh(III)-Catalyzed [5+2] Oxidative Annulation of Cyclic Arylguanidines and Alkynes to 1,3-Benzodiazepines. A Striking Mechanistic Proposal from DFT. Org. Lett. 21, 6, 1779-1783. [doi: 10.1021/acs.orglett.9b00354]. This article may be used for non-commercial purposes in accordance with American Chemical Society Terms and Conditions for self-archiving
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Martínez-Yáñez, N., Suárez, J., Cajaraville, A., Varela, J. A., Saá, C. (2019). Rh(III)-Catalyzed [5+2] Oxidative Annulation of Cyclic Arylguanidines and Alkynes to 1,3-Benzodiazepines. A Striking Mechanistic Proposal from DFT. Org. Lett. 21, 6, 1779-1783
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https://doi.org/10.1021/acs.orglett.9b00354Sponsors
This work has received financial support from MINECO (projects CTQ2014-59015R, CTQ2017-87939R and ORFEO-CINQA network CTQ2016-81797-REDC), the Xunta de Galicia (project GRC2014/032, ED431C 2018/04 and Centro singular de investigación de Galicia accreditation 2016–2019, ED431G/09) and the European Union (European Regional Development Fund - ERDF). N. M.-Y. thanks MINECO and Xunta de Galicia for a predoctoral contract
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Copyright © 2019 American Chemical Society. This article may be used for non-commercial purposes in accordance with American Chemical Society Terms and Conditions for self-archiving