SYNTHETIC METHODOLOGY AND NEW BUILDING BLOCKS
Group Leader: Alexandr Shafir
Synthetic methods development can be broadly described as the field of chemistry interested in creating tools for making, breaking and transforming chemical bonds. Methods development has played a key role in many areas of research, including material science and drug design. In fact, pharmaceutical and agrochemical lead discovery will rely on chemical methods to expand the “chemical space”, i.e. structure families available for testing.
Our group combines the design of reactive organic intermediates, particularly those based on halogens, boron and silicon, with catalysis to development new types of C-C and C-X bond forming reactions. In particular, we are interested in exploiting the carbon-iodine unit in iodoarenes to direct new types of C-H functionalization reactions, in which new reactivity is achieved via high-valent iodine(III) intermediates. For example, we recently show that this approach enables the direct C-H propargylation, sulfonallylation, alkylation and benzylation. In our group, method development goes hand in hand with studies of reaction mechanism, whereby we rely heavily on the detection and characterization of reaction intermediates by a variety of techniques, including NMR and X-Ray diffraction. Additionally, we are interested in the development of new metal-based catalytic methods for cross-coupling reaction. A part of our effort is also directed to the development of new heterogeneous chemically active systems, particularly Metal-Organic Frameworks (MOFs).
- Synthetic methods based on the use of hypervalent iodine reagents
- Transition metal catalysis
- Metal-Organic Framework (MOFs): modulated synthesis, linker design and reactivity.
Scientific staff
Alexandr Shafir
Tenured Scientist
alexandr.shafir@iqac.csic.es
Lab people
Wei Wen Chen Chen
Predoctoral Researcher
wei.chen@iqac.csic.es
- From propenolysis to enyne metathesis: tools for expedited assembly of 4a,8a-azaboranaphthalene and extended polycycles with embedded BN
Federica Rulli, Guillem Sanz-Liarte, Pol Roca, Nina Martínez, Víctor Medina, Raimon Puig de la Bellacasa, Alexandr Shafir and Ana B. Cuenca
Chem. Sci., 15, 5674-5680,2024. - Cyclic Homo- and Heterohalogen Di-λ3-diarylhalonium Structures
Wei W. Chen, Margalida Artigues, Mercè Font-Bardia, Ana B. Cuenca and Alexandr Shafir
J. Am. Chem. Soc. 2023
- Exploring the benzylic gem-C(sp3)-Boron-Silicon and Boron-Tin Centers as a Synthetic Platform
Wei Wen Chen, Nahiane Pipaon, Marta Díaz, Anton Cunillera, Laura Rodríguez, Alexandr Shafir and Ana Belén Cuenca
Chem. Sci., 2021,
- Exploring benzylicgem-C(sp3)-boron-silicon and boron-tin centers as a synthetic platform
Chen, W.W., Fernández, N.P., Baranda, M.D., Cunillera, A., Rodríguez, L.G., Shafir, A., Cuenca, A.B.
Chemical Science, 12 (31), pp. 10514-10521. 2021
- Preparation and Synthetic Applicability of Imidazole-Containing Cyclic Iodonium Salts
Antonkin, N.S., Vlasenko, Y.A., Yoshimura, A., Smirnov, V.I., Borodina, T.N., Zhdankin, V.V., Yusubov, M.S., Shafir, A., Postnikov, P.S.
Journal of Organic Chemistry, 86 (10), pp. 7163-7178. 2021
- The Power of Iodane-Guided C−H Coupling: A Group-Transfer Strategy in Which a Halogen Works for Its Money
Chen, W.W., Cuenca, A.B., Shafir, A.
Angewandte Chemie - International Edition, 59 (38), pp. 16294-16309, 2020
- Iodane‐Guided ortho C−H Allylation
Wei W. Chen, Anton Cunillera,Dandan Chen, Sébastien Lethu, Albert López de Moragas, Jun Zhu, Miquel Solà, Ana B. Cuenca, Alexandr Shafir
Angew. Chem. Int. Ed.. 59 (45), pp. 20201-20207. 2020
- Hypervalent iodine in the structure of N-heterocycles: synthesis, structure, and application in organic synthesis
Vlasenko, Y.А., Yusubov, M.S., Shafir, A., Postnikov, P.S.
Chemistry of Heterocyclic Compounds, 2020
- Crystal‐to‐Crystal Synthesis of Photocatalytic Metal–Organic Frameworks for Visible‐Light Reductive Coupling and Mechanistic Investigations
Lluis Gutiérrez, Suvendu Sekhar Mondal, Alberto Bucci, Noufal Kandoth, Eduardo C. Escudero‐Adán, Alexandr Shafir and Julio Lloret‐Fillold
ChemSusChem. doi:10.1002/cssc.202000465
- Stepwise Mechanism for the Bromination of Arenes by a Hypervalent Iodine Reagent
Granados, A., Shafir, A., Arrieta, A., Cossío, F.P., Vallribera, A.
Journal of Organic Chemistry, 85 (4), pp. 2142-2150. 2020
- Screening and Preliminary Biochemical and Biological Studies of [RuCl(p-cymene)(N,N-bis(diphenylphosphino)-isopropylamine)][BF4] in Breast Cancer Models
Corrales Sánchez, V., Nieto-Jiménez, C., Castro-Osma, J.A., De Andrés, F., Pacheco-Liñán, P.J., Bravo, I., Rodríguez Fariñas, N., Niza, E., Domínguez-Jurado, E., Lara-Sánchez, A., Ríos, Á., Gómez Juárez, M., Montero, J.C., Pandiella, A., Shafir, A., Alonso-Moreno, C., Ocaña, A.
ACS Omega, 4 (8), pp. 13005-13014.2019
- Synthesis of Polysubstituted Iodoarenes Enabled by Iterative Iodine‐Directed para and ortho C−H Functionalization
Wu, Y., Bouvet, S., Izquierdo, S., Shafir, A.
Angewandte Chemie - International Edition, 2018
- Fluoro-tagged osmium and iridium nanoparticles in oxidation reactions
Santacruz, L., Donnici, S., Granados, A., Shafir, A., Vallribera, A.
Tetrahedron, 74 (48), pp. 6890-6895. 2018
- Synthesis of Five-Membered Iodine-Nitrogen Heterocycles from Benzimidazole-Based Iodonium Salts
Vlasenko, Y.A., Postnikov, P.S., Trusova, M.E., Shafir, A., Zhdankin, V.V., Yoshimura, A., Yusubov, M.S.
Journal of Organic Chemistry, 83 (19), pp. 12056-12070. 2018
- Versatile IR Spectroscopy Combined with Synchrotron XAS–XRD: Chemical, Electronic, and Structural Insights during Thermal Treatment of MOF Materials
S. Hinokuma, G. Wiker, T. Suganuma, A. Bansode, D. Stoian, S. Caminero Huertas, S. Molina, A. Shafir, M. Rønning, W. van Beek, A. Urakawa
Eur. J. Inorg. Chem. 2018, 1847–1853 (Very Important Paper) - Acid Activation in Phenyliodine Dicarboxylates: Direct Observation, Structures, and Implications
S. Izquierdo, S. Essafi, I. del Rosal, P. Vidossich, R. Pleixats, A. Vallribera, G. Ujaque, A. Lledós, A. Shafir
J. Am. Chem. Soc. 2016, 138, 12747-12750 - NH-heterocyclic aryliodonium salts: Access to N1-aryl-5-iodoimidazoles
Y. Wu, S. Izquierdo, P. Vidossich, A. Lledós, A. Shafir
Angew. Chem. Int. Ed. 2016, 55, 7152-7156. - Modulation by Amino Acids: Toward Superior Control in the Synthesis of Zirconium Metal–Organic Frameworks
O. V. Gutov, S. Molina, E. C. Escudero‐Adán, Alexandr Shafir
Chem. Eur. J. 2016, 22, 13582-13587 - MOF defects under control: insights into the missing linker sites and their implication in the reactivity of Zr-based frameworks
O. Gutov, M. González Hevia, E. Escudero-Adán, A. Shafir
Inorg. Chem. 2015, 54, 8396–8400 - Hypervalent Activation as Key Step for Dehydrogenative ortho C-C Coupling of Iodoarenes
Arenas, L. Broomfield, E. Martin, A. Shafir
Chem. Eur. J. 2015, 21, 18779-18784 - An Alternative to the Classical α-Arylation: The Transfer of an Intact 2-Iodoaryl from ArI(O2CCF3)2Z.
Jia, E. Gálvez, R. M. Sebastián, R. Pleixats, A. Álvarez-Larena, A. Vallribera, A. Shafir
Angew. Chem. Int. Ed. 2014, 53, 11298-11301
- LUPYPLAST: Síntesis de nuevos lubricantes y materiales modificados con carbono a partir de la pirólisis de residuos plásticos. Coordinator: NEOLIQUIDGrant: Colaboración público-privada 2022
Period: 01/12/2023 - 30/11/2026
Funding: 164.156,00€.CPP2022-009909 financiado por MCIU/AEI/10.13039/501100011033 y por la Unión Europea “NextGenerationEU”/PRTR” - Reactividad naciente de los elementos del bloque p: un crisol de enlaces quimicos y arquitecturas moleculares emergentes.
Coordinator: Alexandr Shafir
Grant: PID2020-113661GB-I00 funded by MCIN/ AEI/10.13039/501100011033
Period: 2021-2024
Funding: 160.000,00
