2024
Catalyst–Substrate Pairings for Carbocyclic and Heterocyclic Systems in Atroposelective Quinazolinone Synthesis
Guo M, Miller S. Catalyst–Substrate Pairings for Carbocyclic and Heterocyclic Systems in Atroposelective Quinazolinone Synthesis. ACS Catalysis 2024, 17226-17232. DOI: 10.1021/acscatal.4c05014.Peer-Reviewed Original ResearchChiral phosphoric acidPositive nonlinear effectNon-covalent interactionsQuinazolinone synthesisHeterocyclic systemsCatalyst scaffoldHigh enantioselectivityNitrogen heteroatomsEnantiomeric ratioCatalystReaction developmentCatalytic scaffoldMechanistic studiesEnantioselectivityPhosphoric acidSubstrateCarbocyclesCyclocondensationHeterocyclesHeteroatomsScaffoldsReactionSynthesisReactivityYieldEnantioselective Sulfonimidamide Acylation via a Cinchona Alkaloid-Catalyzed Desymmetrization: Scope, Data Science, and Mechanistic Investigation
Haas B, Lim N, Jermaks J, Gaster E, Guo M, Malig T, Werth J, Zhang H, Toste F, Gosselin F, Miller S, Sigman M. Enantioselective Sulfonimidamide Acylation via a Cinchona Alkaloid-Catalyzed Desymmetrization: Scope, Data Science, and Mechanistic Investigation. Journal Of The American Chemical Society 2024, 146: 8536-8546. PMID: 38480482, PMCID: PMC10990064, DOI: 10.1021/jacs.4c00374.Peer-Reviewed Original ResearchConceptsDensity functional theoryStructure-activity relationshipBis-acylationExcellent yieldsAsymmetric acylationTetrahedral intermediateSynthetic chemistryFunctional theoryMechanistic investigationsReaction kineticsMechanistic studiesSulfonimidamidesDesymmetrizationEnantioselectivityStructural studiesCatalystAcylPharmacophoreCinchonaIntermediateReactionChemistryKineticsYield
2023
Data Science-Enabled Palladium-Catalyzed Enantioselective Aryl-Carbonylation of Sulfonimidamides
van Dijk L, Haas B, Lim N, Clagg K, Dotson J, Treacy S, Piechowicz K, Roytman V, Zhang H, Toste F, Miller S, Gosselin F, Sigman M. Data Science-Enabled Palladium-Catalyzed Enantioselective Aryl-Carbonylation of Sulfonimidamides. Journal Of The American Chemical Society 2023, 145: 20959-20967. PMID: 37656964, DOI: 10.1021/jacs.3c06674.Peer-Reviewed Original ResearchCross-coupling methodsHeteroaryl iodidesLigand descriptorsExcellent yieldsCoupling partnersChemical spaceMedicinal chemistrySulfonimidamidesAgrochemical discoveryVirtual libraryReaction optimizationOptimal conditionsEfficient strategyHeteroarylScience techniquesEnantioselectivityArylCatalystIodideReactionChemistryData science techniquesYieldDescriptorsDiverse set
2018
Parameterization and Analysis of Peptide-Based Catalysts for the Atroposelective Bromination of 3‑Arylquinazolin-4(3H)‑ones
Crawford JM, Stone EA, Metrano AJ, Miller SJ, Sigman MS. Parameterization and Analysis of Peptide-Based Catalysts for the Atroposelective Bromination of 3‑Arylquinazolin-4(3H)‑ones. Journal Of The American Chemical Society 2018, 140: 868-871. PMID: 29300461, PMCID: PMC5817992, DOI: 10.1021/jacs.7b11303.Peer-Reviewed Original Research
2017
A bottom up approach towards artificial oxygenases by combining iron coordination complexes and peptides
Cussó O, Giuliano MW, Ribas X, Miller SJ, Costas M. A bottom up approach towards artificial oxygenases by combining iron coordination complexes and peptides. Chemical Science 2017, 8: 3660-3667. PMID: 29270284, PMCID: PMC5734052, DOI: 10.1039/c7sc00099e.Peer-Reviewed Original ResearchIron centerHigh enantioselectivityIron coordination complexesAqueous hydrogen peroxideSecond coordination sphereΒ-turn structureShort reaction timesTerminal carboxylic acidSupramolecular catalystsCoordination complexesSupramolecular systemsClasses of substratesAsymmetric catalysisCoordination sphereAsymmetric epoxidationExcellent yieldsCarboxylic acidsCombination of peptidesActivation stepHydrogen peroxideReaction timeEpoxidationEnantioselectivityPeptidesCatalyst
2015
Enantioselective Synthesis of 3‑Arylquinazolin-4(3H)‑ones via Peptide-Catalyzed Atroposelective Bromination
Diener ME, Metrano AJ, Kusano S, Miller SJ. Enantioselective Synthesis of 3‑Arylquinazolin-4(3H)‑ones via Peptide-Catalyzed Atroposelective Bromination. Journal Of The American Chemical Society 2015, 137: 12369-12377. PMID: 26343278, PMCID: PMC5134330, DOI: 10.1021/jacs.5b07726.Peer-Reviewed Original ResearchConceptsAtroposelective brominationDensity functional theory calculationsBroad substrate scopeX-ray crystallographyΒ-turn peptideFunctional theory calculationsCross-coupling sequenceFree catalystsSubstrate scopeAmination procedureStereochemical informationEnantioselective synthesisTheory calculationsHigh enantioselectivityRotational barriersMechanistic studiesSubsequent transformationBrominationMono-orthoProduct of interestCatalystEnantioinductionCrystallographyEnantioselectivityIsomersPhosphothreonine as a Catalytic Residue in Peptide‐Mediated Asymmetric Transfer Hydrogenations of 8‐Aminoquinolines
Shugrue CR, Miller SJ. Phosphothreonine as a Catalytic Residue in Peptide‐Mediated Asymmetric Transfer Hydrogenations of 8‐Aminoquinolines. Angewandte Chemie International Edition 2015, 54: 11173-11176. PMID: 26246129, PMCID: PMC4628550, DOI: 10.1002/anie.201505898.Peer-Reviewed Original ResearchConceptsTransfer hydrogenationChiral phosphoric acid catalystHydrogen bonding interactionsPhosphoric acid catalystAsymmetric transfer hydrogenationEnantioselective transfer hydrogenationAsymmetric catalystsAcid catalystStrong complexationNMR studiesSubstrate classesCatalystHydrogenationNew classCatalytic residuesPeptidesComplexationEnantioselectivityQuinolinePhosphopeptidesSubstrateResidues
2014
Catalyst Control over Regio- and Enantioselectivity in Baeyer–Villiger Oxidations of Functionalized Ketones
Romney DK, Colvin SM, Miller SJ. Catalyst Control over Regio- and Enantioselectivity in Baeyer–Villiger Oxidations of Functionalized Ketones. Journal Of The American Chemical Society 2014, 136: 14019-14022. PMID: 25250713, PMCID: PMC4195385, DOI: 10.1021/ja508757g.Peer-Reviewed Original ResearchConceptsBaeyer-Villiger oxidationPeptide-based catalystsHydrogen bonding interactionsTypes of selectivityParallel kinetic resolutionCatalyst controlFunctionalized KetonesCyclic ketonesFunctional groupsNatural productsComplex moleculesKinetic resolutionAsymmetric processEnantioselectivityRegioKetonesOxidationBroad utilityCatalystCatalysisSelectivityAmidesSynthesisMoleculesProducts