Repositori URV

Author, as appears in the article.: Wahlers J; Margalef J; Hansen E; Bayesteh A; Helquist P; Diéguez M; Pàmies O; Wiest O; Norrby P-O

Department: Química Física i Inorgànica

URV's Author/s: Diéguez Fernández, Montserrat / Margalef Pallarès, Jèssica / Pamies Ollé, Oscar

Keywords: Stereochemistry Prediction Palladium Molecular mechanics Molecular analysis Mechanics Ligand Follow up Experimental study Enantiomer Drug synthesis Conformational transition Chemistry Catalysis Article Amination

Abstract: The palladium-catalyzed enantioselective allylic substitution by carbon or nitrogen nucleophiles is a key transformation that is particularly useful for the synthesis of bioactive compounds. Unfortunately, the selection of a suitable ligand/substrate combination often requires significant screening effort. Here, we show that a transition state force field (TSFF) derived by the quantum-guided molecular mechanics (Q2MM) method can be used to rapidly screen ligand/substrate combinations. Testing of this method on 77 literature reactions revealed several cases where the computationally predicted major enantiomer differed from the one reported. Interestingly, experimental follow-up led to a reassignment of the experimentally observed configuration. This result demonstrates the power of mechanistically based methods to predict and, where necessary, correct the stereochemical outcome. © 2021, The Author(s).

Thematic Areas: Zootecnia / recursos pesqueiros Saúde coletiva Química Psicología Planejamento urbano e regional / demografia Physics and astronomy (miscellaneous) Physics and astronomy (all) Odontología Nutrição Multidisciplinary sciences Multidisciplinary Medicina veterinaria Medicina iii Medicina ii Medicina i Materiais Matemática / probabilidade e estatística Interdisciplinar Geociências General physics and astronomy General medicine General chemistry General biochemistry,genetics and molecular biology Farmacia Engenharias iv Educação física Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências ambientais Ciências agrárias i Ciência da computação Chemistry (miscellaneous) Chemistry (all) Biotecnología Biodiversidade Biochemistry, genetics and molecular biology (miscellaneous) Biochemistry, genetics and molecular biology (all) Astronomia / física Antropologia / arqueologia

licence for use: https://creativecommons.org/licenses/by/3.0/es/

Author's mail: oscar.pamies@urv.cat montserrat.dieguez@urv.cat

Author identifier: 0000-0002-2352-8508 0000-0002-8450-0656

Record's date: 2024-07-27

Papper version: info:eu-repo/semantics/publishedVersion

Link to the original source: https://www.nature.com/articles/s41467-021-27065-2

Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/

Papper original source: Nature Communications. 12 (1):

APA: Wahlers J; Margalef J; Hansen E; Bayesteh A; Helquist P; Diéguez M; Pàmies O; Wiest O; Norrby P-O (2021). Proofreading experimentally assigned stereochemistry through Q2MM predictions in Pd-catalyzed allylic aminations. Nature Communications, 12(1), -. DOI: 10.1038/s41467-021-27065-2

Article's DOI: 10.1038/s41467-021-27065-2

Entity: Universitat Rovira i Virgili

Journal publication year: 2021

Publication Type: Journal Publications