2026-04-22T22:53:35Zhttps://riubu.ubu.es/oai/request

oai:riubu.ubu.es:10259/113342026-02-07T01:05:23Zcom_10259_4363com_10259_5086com_10259_2604col_10259_4364

One-pot photocatalytic transformation of indolines into 3-thiocyanate indoles with new Ir(iii) photosensitizers bearing β-carbolines Sanz Villafruela, Juan Martínez Alonso, Carmen Echevarría Poza, Igor Vaquero Gutiérrez, Mónica Carbayo Martín, Mª Aránzazu Fidalgo Zorrilla, Jairo Rodríguez, Ana M. Cuevas Vicario, José Vicente Lima, João C. Moro, Artur J. Manzano Manrique, Blanca Rosa Jalón Sotés, Félix Ángel Espino Ordóñez, Gustavo Photocatalysis Singlet oxygen Iridium(III) photocatalysts Thiocyanation of indoles Photooxidative dehydrogenation of indolines β-carbolines Química orgánica Química física Chemistry, Organic Chemistry, Physical and theoretical Current societies demand sustainable synthetic procedures and accordingly the combination of two photocatalytic reactions in a one-pot process is a very appealing chemical tool. In the present work, we report on the development of new Ir(III) bis-cyclometallated photosensitizers with β-carboline ligands and disclose a simple and unprecedented photocatalytic one-pot two-step protocol for the chemoselective and C-3 regioselective oxidative thiocyanation of indolines to produce the corresponding 3-thiocyanato-indoles. The procedure is performed in THF at room temperature, in the presence of NH4SCN, O2 and the Ir(III) photocatalysts under blue light exposure. Moreover, this methodology combines important advantages such as an outstanding efficiency, based on good yields for low catalyst loadings, along with an excellent sustainability founded on the use of O2 as a green oxidant and light as the energy source. In addition, DFT studies have allowed a clear interpretation of the photophysical and electrochemical properties of the Ir(III) complexes and transient absorption experiments, along with other experimental proof, have demonstrated that the two photocatalytic processes are mediated by 1O2. Our results pave the way for future developments in the field of photocatalysis using Ir(III) biscyclometallated complexes as photosensitizers. We gratefully acknowledge the financial support provided by the Spanish Ministerio de Ciencia, Innovación y Universidades (RTI2018-100709-B-C21, CTQ (QMC)-RED2018-102471-T and PID2019-111215RB-I00), Junta de Castilla y León (BU087G19, Grant BU263P18) and Junta de Comunidades de Castilla-La Mancha-FEDER (JCCM) (grant SBPLY/19/180501/000260). J. Fidalgo and I. Echevarría want to acknowledge their fellowships to both the European Social Fund (ESF) and Consejería de Educación de la Junta de Castilla y León and J. Sanz-Villafruela to a fellowship from the ESF and the Plan Propio of the University of Castilla-La Mancha. M. V. (Prof. B. García Group, University of Burgos) is grateful for the financial support received from the Consejería de Educación-Junta de Castilla y León-FEDER (BU042U16-BU305P18) for the postdoctoral grant. This research has made use of the high-performance computing resources of the Castilla y León Supercomputing Center (SCAYLE, https://www.scayle.es), financed by FEDER (Fondo Europeo de Desarrollo Regional). 2026-02-06T11:36:50Z 2026-02-06T11:36:50Z 2021 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion 2052-1553 https://hdl.handle.net/10259/11334 10.1039/d0qi01307b 2052-1553 eng Inorganic Chemistry Frontiers. 2021, V. 8, n. 5, p. 1253-1270 https://doi.org/10.1039/D0QI01307B info:eu-repo/semantics/openAccess application/pdf Royal Society of Chemistry https://riubu.ubu.es/bitstream/10259/11334/3/Sanz-icf_2021.pdf.jpg Hispana TEXT http://rightsstatements.org/vocab/CNE/1.0/ RIUBU. Repositorio Institucional de la Universidad de Burgos https://hdl.handle.net/10259/11334