2024
Catalytic Enantioselective Sulfoxidation of Functionalized Thioethers Mediated by Aspartic Acid-Containing Peptides
Huth S, Tampellini N, Guerrero M, Miller S. Catalytic Enantioselective Sulfoxidation of Functionalized Thioethers Mediated by Aspartic Acid-Containing Peptides. Organic Letters 2024, 26: 6872-6877. PMID: 39102356, PMCID: PMC11329351, DOI: 10.1021/acs.orglett.4c02452.Peer-Reviewed Original ResearchConceptsEnantioselective oxidation of sulfidesModel of transition stateLevels of enantioinductionOxidation of sulfidesChiral sulfoxidesPeptide catalystsTransition stateEnantioselective sulfoxidationAspartic acid-containing peptidesSulfoxideThioethersEnantioinductionCatalystMoietySubstrateHydrogenSulfideExperimental evidence
2018
Rapid phenolic O-glycosylation of small molecules and complex unprotected peptides in aqueous solvent
Wadzinski TJ, Steinauer A, Hie L, Pelletier G, Schepartz A, Miller SJ. Rapid phenolic O-glycosylation of small molecules and complex unprotected peptides in aqueous solvent. Nature Chemistry 2018, 10: 644-652. PMID: 29713033, PMCID: PMC5964040, DOI: 10.1038/s41557-018-0041-8.Peer-Reviewed Original ResearchConceptsUnprotected peptidesSmall moleculesAmino acid functionalitiesHigh functional group toleranceFunctional group toleranceFree synthesisAcid functionalityProteinogenic amino acidsAqueous solventSelective formationSynthetic glycopeptidesAnomeric productsPhenolic functionalityGroup toleranceNatural productsGood yieldsSide chainsGlycosyl donorsBiochemical probesAryl glycosidesRoom temperatureMoleculesO-glycosylationPeptidesSimple approachDisulfide-Bridged Peptides That Mediate Enantioselective Cycloadditions through Thiyl Radical Catalysis
Ryss JM, Turek AK, Miller SJ. Disulfide-Bridged Peptides That Mediate Enantioselective Cycloadditions through Thiyl Radical Catalysis. Organic Letters 2018, 20: 1621-1625. PMID: 29504763, PMCID: PMC5963541, DOI: 10.1021/acs.orglett.8b00364.Peer-Reviewed Original ResearchParameterization 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
Enantioselective Intermolecular C–O Bond Formation in the Desymmetrization of Diarylmethines Employing a Guanidinylated Peptide-Based Catalyst
Chinn AJ, Kim B, Kwon Y, Miller SJ. Enantioselective Intermolecular C–O Bond Formation in the Desymmetrization of Diarylmethines Employing a Guanidinylated Peptide-Based Catalyst. Journal Of The American Chemical Society 2017, 139: 18107-18114. PMID: 29116792, PMCID: PMC5738244, DOI: 10.1021/jacs.7b11197.Peer-Reviewed Original ResearchConceptsComplex molecular settingsO bond formationPeptide-based ligandsCross-coupling reactionsPhenolic hydroxyl groupsIntermolecular CuIntermolecular CChemoselective reactionTBu groupBond formationAppreciable selectivityReactive sitesPhenolic nucleophilesHydroxyl groupsSteric perturbationsMaximum enantioselectivitySecond reactive siteMolecular settingNucleophilesDesymmetrizationUncommon levelReactionSubstrateCatalystChemistryDesymmetrization of Diarylmethylamido Bis(phenols) through Peptide-Catalyzed Bromination: Enantiodivergence as a Consequence of a 2 amu Alteration at an Achiral Residue within the Catalyst
Hurtley AE, Stone EA, Metrano AJ, Miller SJ. Desymmetrization of Diarylmethylamido Bis(phenols) through Peptide-Catalyzed Bromination: Enantiodivergence as a Consequence of a 2 amu Alteration at an Achiral Residue within the Catalyst. The Journal Of Organic Chemistry 2017, 82: 11326-11336. PMID: 29020446, PMCID: PMC5738245, DOI: 10.1021/acs.joc.7b02339.Peer-Reviewed Original Research
2016
Diversity of Secondary Structure in Catalytic Peptides with β‑Turn-Biased Sequences
Metrano AJ, Abascal NC, Mercado BQ, Paulson EK, Hurtley AE, Miller SJ. Diversity of Secondary Structure in Catalytic Peptides with β‑Turn-Biased Sequences. Journal Of The American Chemical Society 2016, 139: 492-516. PMID: 28029251, PMCID: PMC5312972, DOI: 10.1021/jacs.6b11348.Peer-Reviewed Original ResearchMeSH KeywordsCatalysisCrystallography, X-RayModels, MolecularPeptidesProtein ConformationQuantum TheoryConceptsPeptide-based catalystsSolid-state structural featuresΒ-turn secondary structureX-ray crystal structureProton chemical shiftsCorresponding solution structuresSymmetry-independent moleculesX-ray crystallographyAccessible transition stateGround state conformationSeries of tetrapeptidesChemical shiftsDifferent peptide sequencesEnantioselective reactionsSecondary structureCatalytic activityBromination reactionSame unit cellCatalytic peptidesTransition stateCrystal structureCatalystState conformationComputational studyConformational equilibriumSolution Structures and Molecular Associations of a Peptide-Based Catalyst for the Stereoselective Baeyer–Villiger Oxidation
Abascal NC, Miller SJ. Solution Structures and Molecular Associations of a Peptide-Based Catalyst for the Stereoselective Baeyer–Villiger Oxidation. Organic Letters 2016, 18: 4646-4649. PMID: 27588823, PMCID: PMC5130343, DOI: 10.1021/acs.orglett.6b02282.Peer-Reviewed Original ResearchConceptsBaeyer-Villiger oxidationPeptide-based catalystsStereoselective Baeyer–Villiger oxidationsCatalytic reactionStereoselective catalystsEffect of additivesSolution conformationCatalystMolecular associationSubstrate-specific interactionsUnique structureSolution structureOxidationStructural analysisAdvantageous featuresSelectivityExperimental observationsPeptidesConformationStructureAdditivesReactionSynthesis and evaluation of phenylalanine-derived trifluoromethyl ketones for peptide-based oxidation catalysis
Featherston AL, Miller SJ. Synthesis and evaluation of phenylalanine-derived trifluoromethyl ketones for peptide-based oxidation catalysis. Bioorganic & Medicinal Chemistry 2016, 24: 4871-4874. PMID: 27452284, PMCID: PMC5053897, DOI: 10.1016/j.bmc.2016.07.012.Peer-Reviewed Original ResearchDistal Stereocontrol Using Guanidinylated Peptides as Multifunctional Ligands: Desymmetrization of Diarylmethanes via Ullman Cross-Coupling
Kim B, Chinn AJ, Fandrick DR, Senanayake CH, Singer RA, Miller SJ. Distal Stereocontrol Using Guanidinylated Peptides as Multifunctional Ligands: Desymmetrization of Diarylmethanes via Ullman Cross-Coupling. Journal Of The American Chemical Society 2016, 138: 7939-7945. PMID: 27254785, PMCID: PMC5127171, DOI: 10.1021/jacs.6b03444.Peer-Reviewed Original Research
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 interestCatalystEnantioinductionCrystallographyEnantioselectivityIsomersImproved Carbohydrate Recognition in Water with an Electrostatically Enhanced β‑Peptide Bundle
Melicher MS, Walker AS, Shen J, Miller SJ, Schepartz A. Improved Carbohydrate Recognition in Water with an Electrostatically Enhanced β‑Peptide Bundle. Organic Letters 2015, 17: 4718-4721. PMID: 26376076, DOI: 10.1021/acs.orglett.5b02187.Peer-Reviewed Original ResearchSite-Selective Reactions with Peptide-Based Catalysts
Giuliano MW, Miller SJ. Site-Selective Reactions with Peptide-Based Catalysts. 2015, 372: 157-201. PMID: 26307403, DOI: 10.1007/128_2015_653.Peer-Reviewed Original ResearchPhosphothreonine 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 ResearchMeSH KeywordsCatalysisKetonesKineticsOxidation-ReductionPeptidesStereoisomerismSubstrate SpecificityConceptsBaeyer-Villiger oxidationPeptide-based catalystsHydrogen bonding interactionsTypes of selectivityParallel kinetic resolutionCatalyst controlFunctionalized KetonesCyclic ketonesFunctional groupsNatural productsComplex moleculesKinetic resolutionAsymmetric processEnantioselectivityRegioKetonesOxidationBroad utilityCatalystCatalysisSelectivityAmidesSynthesisMoleculesProductsExperimental Lineage and Functional Analysis of a Remotely Directed Peptide Epoxidation Catalyst
Lichtor PA, Miller SJ. Experimental Lineage and Functional Analysis of a Remotely Directed Peptide Epoxidation Catalyst. Journal Of The American Chemical Society 2014, 136: 5301-5308. PMID: 24690108, PMCID: PMC4333582, DOI: 10.1021/ja410567a.Peer-Reviewed Original ResearchDiastereo- and Enantioselective Addition of Anilide-Functionalized Allenoates to N‑Acylimines Catalyzed by a Pyridylalanine-Based Peptide
Mbofana CT, Miller SJ. Diastereo- and Enantioselective Addition of Anilide-Functionalized Allenoates to N‑Acylimines Catalyzed by a Pyridylalanine-Based Peptide. Journal Of The American Chemical Society 2014, 136: 3285-3292. PMID: 24527787, DOI: 10.1021/ja412996f.Peer-Reviewed Original ResearchPeptide-Catalyzed Conversion of Racemic Oxazol-5(4H)‑ones into Enantiomerically Enriched α‑Amino Acid Derivatives
Metrano AJ, Miller SJ. Peptide-Catalyzed Conversion of Racemic Oxazol-5(4H)‑ones into Enantiomerically Enriched α‑Amino Acid Derivatives. The Journal Of Organic Chemistry 2014, 79: 1542-1554. PMID: 24517453, DOI: 10.1021/jo402828f.Peer-Reviewed Original Research
2013
A β‑Boronopeptide Bundle of Known Structure As a Vehicle for Polyol Recognition
Melicher MS, Chu J, Walker AS, Miller SJ, Baxter RH, Schepartz A. A β‑Boronopeptide Bundle of Known Structure As a Vehicle for Polyol Recognition. Organic Letters 2013, 15: 5048-5051. PMID: 24032486, DOI: 10.1021/ol402381n.Peer-Reviewed Original ResearchEnantioselective Synthesis of Atropisomeric Benzamides through Peptide-Catalyzed Bromination
Barrett KT, Miller SJ. Enantioselective Synthesis of Atropisomeric Benzamides through Peptide-Catalyzed Bromination. Journal Of The American Chemical Society 2013, 135: 2963-2966. PMID: 23410090, PMCID: PMC3596792, DOI: 10.1021/ja400082x.Peer-Reviewed Original ResearchConceptsEnantioselective synthesisElectrophilic aromatic substitution reactionsSeries of triAromatic substitution reactionMetal-halogen exchangeRange of compoundsCatalytic brominationNMR spectroscopySubstitution reactionsBrønsted baseObserved productsOrtho functionalizationTertiary aminesLow conversionSubstitution patternBrominationCatalystHigh barrierBenzamidesReactionTertiary benzamidesAppropriate substrateSynthesisFunctionalizationDibromination