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Mapping Catalyst–Solvent Interplay in Competing Carboamination/Cyclopropanation Reactions
Author(s) -
Wodrich Matthew D.,
Chang Miyeon,
Gallarati Simone,
Woźniak Łukasz,
Cramer Nicolai,
Corminboeuf Clemence
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202200399
Subject(s) - cyclopropanation , catalysis , chemistry , solvent , selectivity , cyclopentadienyl complex , reactivity (psychology) , combinatorial chemistry , organic chemistry , medicine , alternative medicine , pathology
Abstract Group 9 metals, in particular Rh III complexes with cyclopentadienyl ligands, are competent C−H activation catalysts. Recently, a Cp*Rh III ‐catalyzed reaction of alkenes with N ‐enoxyphthalimides showed divergent outcome based on the solvent, with carboamination favored in methanol and cyclopropanation in 2,2,2‐trifluoroethanol (TFE). Here, we create selectivity and activity maps capable of unravelling the catalyst‐solvent interplay on the outcome of these competing reactions by analyzing 42 cyclopentadienyl metal catalysts, Cp X M III (M=Co, Rh, Ir). These maps not only can be used to rationalize previously reported experimental results, but also capably predict the behavior of untested catalyst/solvent combinations as well as aid in identifying experimental protocols that simultaneously optimize both catalytic activity and selectivity (solutions in the Pareto front). In this regard, we demonstrate how and why the experimentally employed Cp*Rh III catalyst represents an ideal choice to invoke a solvent‐induced change in reactivity. Additionally, the maps reveal the degree to which even perceived minor changes in the solvent (e. g., replacing methanol with ethanol) influence the ratio of carboamination and cyclopropanation products. Overall, the selectivity and activity maps presented here provide a generalizable tool to create global pictures of anticipated reaction outcome that can be used to develop new experimental protocols spanning metal, ligand, and solvent space.