ja8b04243_si_003.xlsx (525.96 kB)
Stereodivergent Rhodium(III)-Catalyzed cis-Cyclopropanation Enabled by Multivariate Optimization
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posted on 2018-07-23, 04:30 authored by Tiffany Piou, Fedor Romanov-Michailidis, Melissa A. Ashley, Maria Romanova-Michaelides, Tomislav RovisThe design of stereodivergent
transformations is of great interest
to the synthetic community as it allows funneling of a given reaction
pathway toward one stereochemical outcome or another by only minor
adjustments of the reaction setup. Herein, we present a physical organic
approach to invert the sense of induction in diastereoselective cyclopropanation
of alkenes with N-enoxyphthalimides through
rhodium(III) catalysis. Careful parametrization of catalyst–substrate
molecular determinants allowed us to interrogate linear-free energy
relationships and establish an intuitive and robust statistical model
that correlates an extensive number of data points in high accuracy.
Our multivariate correlations-steered mechanistic investigation culminated
with a robust and general diastereodivergent cyclopropanation
tool where the switch from trans- to cis-diastereoinduction is attributed to a mechanistic dichotomy.
Selectivity might be determined by the flexibility of rhodacyclic
intermediates derived from ring-opened versus -unopened phthalimides,
induced by both their respective ring size and the Sterimol B1 parameter of the CpX ligand on rhodium.
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Stereodivergentenoxystereochemical outcomealkeneinductiondiastereoselective cyclopropanationring sizereaction setupCareful parametrizationdichotomymultivariate correlations-steeredCp X ligandRhodiumlinear-free energy relationshipsinvestigationapproachrhodiumMultivariate OptimizationciSterimol B 1 parameterflexibilitydeterminantdata pointscatalysitoolring-openedEnabledcatalystSelectivityrhodacyclic intermediatescis-Cyclopropanationstereodivergent transformationsaccuracycorrelateHereinphthalimidemodelreaction pathway
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