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 ResearchConceptsReductive 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 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 ResearchMeSH KeywordsCatalysisHalogenationModels, MolecularPeptidesProtein Conformation, beta-StrandQuinazolinonesStereoisomerism
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 StructurePeptidesPhenolsStereoisomerismStereodynamic Quinone–Hydroquinone Molecules That Enantiomerize at sp3‑Carbon via Redox-Interconversion
Kim B, Storch G, Banerjee G, Mercado BQ, Castillo-Lora J, Brudvig GW, Mayer JM, Miller SJ. Stereodynamic Quinone–Hydroquinone Molecules That Enantiomerize at sp3‑Carbon via Redox-Interconversion. Journal Of The American Chemical Society 2017, 139: 15239-15244. PMID: 28931280, PMCID: PMC5735348, DOI: 10.1021/jacs.7b09176.Peer-Reviewed Original ResearchConceptsRedox-active substituentsStereogenic carbon atomCarbon-bearing moleculesFunctional group migrationRedox interconversionChiral compoundsOrganic moleculesMolecular chiralityDifferent substituentsHydroquinone groupsSp3 carbonCarbon centerEnantiomerization pathwayMaterials scienceCarbon atomsChemical processesConstituent bondsGroup migrationMoleculesDeracemization processSubstituentsBondsChiralityCompoundsEnantiomerizationPursuit 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 observationsPeptidesConformationStructureAdditivesReactionDistal 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 interestCatalystEnantioinductionCrystallographyEnantioselectivityIsomersRegioselective 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 ResearchConceptsLithium-halogen exchangeAsymmetric ligandsBenzamide scaffoldChiral moleculesRegioselective derivatizationEnantioselective synthesisGroup installationRegioselective transformationSequential PdAllylic alkylationHigh regioselectivityMoleculesBenzamidesPhosphinoDerivatizationRegioselectivityAlkylationLigandsTribromideSynthesisDerivativesPdScaffoldsPotential utility
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 utilityCatalystCatalysisSelectivityAmidesSynthesisMoleculesProductsTotal 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 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
The Roles of Counterion and Water in a Stereoselective Cysteine‐Catalyzed Rauhut–Currier Reaction: A Challenge for Computational Chemistry
Osuna S, Dermenci A, Miller SJ, Houk KN. The Roles of Counterion and Water in a Stereoselective Cysteine‐Catalyzed Rauhut–Currier Reaction: A Challenge for Computational Chemistry. Chemistry - A European Journal 2013, 19: 14245-14253. PMID: 24038400, PMCID: PMC3918516, DOI: 10.1002/chem.201300745.Peer-Reviewed Original ResearchMeSH KeywordsCatalysisCysteineIonsMolecular Dynamics SimulationMolecular StructurePotassiumSodiumStereoisomerismWaterConceptsRauhut-Currier reactionCysteine derivativesComplete reaction pathwayRole of counterionsPresence of counterionsRate-determining eliminationMichael addition productsDensity functional theoryComputational chemistryExplicit water solvationWater solvationPotassium counterionsReaction conditionsReaction pathwaysAddition productsEnantiomer pairsThiol catalystCatalyst eliminationPossible stereoisomersCurrier ReactionFunctional theoryCounterionsNucleophilesReactionDerivativesEnantioselective 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