Martínez Yáñez, NuriaSuárez Rivero, JaimeCajaraville Leiro, AnaVarela Carrete, Jesús ÁngelSaá Rodríguez, Carlos2020-10-052020-10-052019Martínez-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, 1779-17831523-7060http://hdl.handle.net/10347/23354NOTICE: 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-archivingA 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.engCopyright © 2019 American Chemical Society. This article may be used for non-commercial purposes in accordance with American Chemical Society Terms and Conditions for self-archivingAlkynesArylguanidines1,3-BenzodiazepinesOxidative AnnulationRhodiumjournal article10.1021/acs.orglett.9b003541523-7052open access