RT Journal Article
T1 Rh(III)-Catalyzed [5+2] Oxidative Annulation of Cyclic Arylguanidines and Alkynes to 1,3-Benzodiazepines. A Striking Mechanistic Proposal from DFT
A1 Martínez Yáñez, Nuria
A1 Suárez Rivero, Jaime
A1 Cajaraville Leiro, Ana
A1 Varela Carrete, Jesús Ángel
A1 Saá Rodríguez, Carlos
K1 Alkynes
K1 Arylguanidines
K1 1,3-Benzodiazepines
K1 Oxidative Annulation
K1 Rhodium
AB 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.
PB American Chemical Society
SN 1523-7060
YR 2019
FD 2019
LK http://hdl.handle.net/10347/23354
UL http://hdl.handle.net/10347/23354
LA eng
NO 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
NO 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
NO 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
DS Minerva
RD 24 abr 2026