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 ResearchMeSH KeywordsAspartic AcidCatalysisHydrogen BondingMolecular StructureOxidation-ReductionPeptidesStereoisomerismSulfidesSulfoxidesConceptsEnantioselective oxidation of sulfidesModel of transition stateLevels of enantioinductionOxidation of sulfidesChiral sulfoxidesPeptide catalystsTransition stateEnantioselective sulfoxidationAspartic acid-containing peptidesSulfoxideThioethersEnantioinductionCatalystMoietySubstrateHydrogenSulfideExperimental evidenceEnantioselective 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
2018
Divergent Control of Point and Axial Stereogenicity: Catalytic Enantioselective C−N Bond‐Forming Cross‐Coupling and Catalyst‐Controlled Atroposelective Cyclodehydration
Kwon Y, Chinn AJ, Kim B, Miller SJ. Divergent Control of Point and Axial Stereogenicity: Catalytic Enantioselective C−N Bond‐Forming Cross‐Coupling and Catalyst‐Controlled Atroposelective Cyclodehydration. Angewandte Chemie International Edition 2018, 57: 6251-6255. PMID: 29637680, PMCID: PMC5964046, DOI: 10.1002/anie.201802963.Peer-Reviewed Original ResearchMeSH KeywordsCatalysisCopperDehydrationHeterocyclic CompoundsMolecular StructureOrganometallic CompoundsPhosphoric AcidsStereoisomerismConceptsAxis of chiralityCopper complexesChiral phosphoric acid catalystChiral copper complexesPhosphoric acid catalystStereogenic carbon centersMultiple stereoisomersCatalytic approachCatalytic reactionStereogenic elementsAcid catalystRemote desymmetrizationCatalyst controlAxial chiralityCarbon centerStereogenic centersCross couplingHigh diastereoselectivityPhosphoric acidCatalystChiralityStereoisomersCyclodehydrationStereogenicityReactionDivergent Stereoselectivity in Phosphothreonine (pThr)-Catalyzed Reductive Aminations of 3‑Amidocyclohexanones
Shugrue C, Featherston AL, Lackner RM, Lin A, Miller SJ. Divergent Stereoselectivity in Phosphothreonine (pThr)-Catalyzed Reductive Aminations of 3‑Amidocyclohexanones. The Journal Of Organic Chemistry 2018, 83: 4491-4504. PMID: 29547285, PMCID: PMC5963540, DOI: 10.1021/acs.joc.8b00207.Peer-Reviewed Original ResearchMeSH KeywordsAminationBiological ProductsCatalysisCyclohexanonesKineticsMolecular StructureOxidation-ReductionPhosphothreonineQuantum TheoryStereoisomerismConceptsReductive aminationNumerous reactive sitesPeptide catalystsParallel kinetic resolutionDFT calculationsNMR studiesReactive sitesDivergent selectivitySecondary interactionsNatural productsKinetic resolutionCatalystAminationDivergent stereoselectivitiesCatalyzed Reductive AminationPeptide sequencesSelectivityComplex substratesSubstrateDiastereoselectivityStereoselectivityProductsReactivityPhosphopeptidesPhosphothreonineDisulfide-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 Research
2017
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
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 ResearchMeSH KeywordsCatalysisCrystallography, X-RayHalogenationKineticsModels, MolecularMolecular StructurePeptidesPhenolsStereoisomerismPursuit of Noncovalent Interactions for Strategic Site-Selective Catalysis
Toste FD, Sigman MS, Miller SJ. Pursuit of Noncovalent Interactions for Strategic Site-Selective Catalysis. Accounts Of Chemical Research 2017, 50: 609-615. PMID: 28945415, PMCID: PMC5643260, DOI: 10.1021/acs.accounts.6b00613.Peer-Reviewed Original Research
2016
Solution 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 ResearchMeSH KeywordsCatalysisCyclohexanonesMolecular StructureOxidation-ReductionPeptidesSolutionsStereoisomerismConceptsBaeyer-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 ResearchMeSH KeywordsCatalysisCrystallography, X-RayEpoxy CompoundsKetonesModels, MolecularMolecular StructureOxidation-ReductionPeptidesPhenylalanineDistal 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 ResearchMeSH KeywordsCarbohydratesFructoseGlucoseMolecular StructureOligosaccharidesPeptidesSolventsSorbitolStatic ElectricityThermodynamicsWaterStructure Diversification of Vancomycin through Peptide-Catalyzed, Site-Selective Lipidation: A Catalysis-Based Approach To Combat Glycopeptide-Resistant Pathogens
Yoganathan S, Miller SJ. Structure Diversification of Vancomycin through Peptide-Catalyzed, Site-Selective Lipidation: A Catalysis-Based Approach To Combat Glycopeptide-Resistant Pathogens. Journal Of Medicinal Chemistry 2015, 58: 2367-2377. PMID: 25671771, PMCID: PMC4364393, DOI: 10.1021/jm501872s.Peer-Reviewed Original ResearchConceptsStructure diversificationLipid chain lengthStructure-activity relationship studiesPeptide catalystsCatalytic approachAliphatic hydroxylDerivatization sitesDerivatives 9aGlycopeptide-resistant pathogensNovel antibiotic leadsChain lengthLipid chainsRelationship studiesAntibiotic leadsCatalystCatalysisAntibiotic-resistant infectionsHydroxylHereinScaffoldsBioactivityChainSpectraLipidationIncorporationRegioselective Derivatizations of a Tribrominated Atropisomeric Benzamide Scaffold
Barrett KT, Miller SJ. Regioselective Derivatizations of a Tribrominated Atropisomeric Benzamide Scaffold. Organic Letters 2015, 17: 580-583. PMID: 25582814, PMCID: PMC4364386, DOI: 10.1021/ol503593y.Peer-Reviewed Original ResearchMeSH KeywordsAlkylationBenzamidesCatalysisCombinatorial Chemistry TechniquesHydrocarbons, BrominatedMolecular StructurePalladiumStereoisomerismConceptsLithium-halogen exchangeAsymmetric ligandsBenzamide scaffoldChiral moleculesRegioselective derivatizationEnantioselective synthesisGroup installationRegioselective transformationSequential PdAllylic alkylationHigh regioselectivityMoleculesBenzamidesPhosphinoDerivatizationRegioselectivityAlkylationLigandsTribromideSynthesisDerivativesPdScaffoldsPotential utility
2014
Total synthesis and isolation of citrinalin and cyclopiamine congeners
Mercado-Marin EV, Garcia-Reynaga P, Romminger S, Pimenta EF, Romney DK, Lodewyk MW, Williams DE, Andersen RJ, Miller SJ, Tantillo DJ, Berlinck RG, Sarpong R. Total synthesis and isolation of citrinalin and cyclopiamine congeners. Nature 2014, 509: 318-324. PMID: 24828190, PMCID: PMC4117207, DOI: 10.1038/nature13273.Peer-Reviewed Original ResearchConceptsNitrogen atomsChemical synthesisMultiple nitrogen atomsBasic nitrogen atomTotal synthesisFunctional groupsNatural productsSelective introductionTarget moleculesSuch compoundsChemical connectionsSynthesisAtomsBiogenetic precursorBasicityCompoundsMoleculesBroad rangePrecursorsAlkaloidsPresenceCongenersProductsSpontaneous transfer of chirality in an atropisomerically enriched two-axis system
Barrett KT, Metrano AJ, Rablen PR, Miller SJ. Spontaneous transfer of chirality in an atropisomerically enriched two-axis system. Nature 2014, 509: 71-75. PMID: 24747399, PMCID: PMC4008667, DOI: 10.1038/nature13189.Peer-Reviewed Original ResearchExperimental 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 Research