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CHIRAL CATALYSTS FOR ENANTIOSELECTIVE SYNTHESES

用于对映选择性合成的手性催化剂

基本信息

批准号：
7471675
负责人：
Michael PATRICK Doyle
金额：
$ 28.44万
依托单位：
UNIV OF MARYLAND, COLLEGE PARK
依托单位国家：
美国
项目类别：
财政年份：
1991
资助国家：
美国
起止时间：
1991-09-01 至 2013-08-31
项目状态：
已结题

来源：
https://reporter.nih.gov/project-details/7471675
关键词：
3-hydroxybutanal Acetates Acetone Acidity Acids Age Alcohols Aldehydes Alder plant Alkenes Ally Amides Amines Area Aromatic Amines Aziridines Benzodiazepines Biological Biological Factors Books Bromides CD3 Antigens Carbon Carbonates Catalysis Characteristics Chemicals Chemistry Chromium Cobalt Collaborations Community Health Nurse Specialist Compatible Complex Condition Copper Coupled Crystallization Cyclization Cyclopropanes DNA Sequence Rearrangement Data Detection Development Diels Alder reaction Discrimination Dissociation Doctor of Philosophy Electron Transport Electronics Employee Strikes Epoxy Compounds Equilibrium Esters Ethers Ethyl Ether Exclusion Facility Construction Funding Category Free Energy Funding Goals Grant Halogens Heterocyclic Compounds High Pressure Liquid Chromatography Hydrogen Hydrogen Peroxide Hydrolysis Hydroxide Ion Hydroxides Imines Individual Investigation Ions Isomerism Isoquinolines Isotopes Ketones Kinetics Laboratories Lactones Lead Ligands Link Manganese Manuscripts Mediating Metals Methodology Methods Modeling Modification Nitrogen Numbers Object Attachment Organic Synthesis Outcome Oxygen Palladium Pathway interactions Phenols Physical condensation Polymers Positioning Attribute Potassium Preparation Principal Investigator Process Proline Publications Publishing Pyrazoles Pyrroles Pyrrolidines Quinine Range Rate Reaction Recovery Reflux Relative (related person)Reporting Research Research Peer Review Resort Rhodium Role Route Ruthenium Scandium Scheme Site Solubility Solvents Standards of Weights and Measures Steroids Sulfonamides System Techniques Temperature Thermodynamics Titanium Toluene Transfer RNA United States National Institutes of Health Unsaturated Fatty Acids Variant Vertebral column Water alkyl group analog azetidinone aziridine base carbene carbonyl compound carboxylate catalyst coping cycloaddition cyclopropane decane deprotonation design desire diazo compound dirhodium tetraacetate dirhodium tetrakis(S-(N-dodecylbenzenesulfonyl)prolinate)enol hydronium ion inhibitor/antagonist insight interest novel oxidation peroxidation prevent programs pyrazole pyridine pyrrolidine pyrroline racemization size sodium ion stereochemistry tert-Butylhydroperoxide tertiary amine tetrahydrofuran ylide

项目摘要

The goal of this research program is the design and development of highly selective and efficient catalytic processes for the synthesis of biologically relevant compounds. Investigations will build upon our newest discoveries with unique catalytic uses of dirhodium carboxamidates. Breakthroughs in their applications for chemical oxidations and as chiral Lewis acids have demonstrated greatly enhanced versatility for these catalysts that will be further explored. The fixed stereodefined geometry of these catalysts provides access to highly enantioenriched products in metal carbene reactions of diazoacetates and, together with their low oxidation potentials, also provides capabilities for highly selective Lewis acid catalyzed reactions and efficient chemical oxidations. In all aims we seek high turnover numbers and high selectivities. In this funding period we will resolve limitations of chiral dirhodium carboxamidates for metal carbene transform- ations by novel processes for which preliminary results indicate that the aims will be achieved. We will develop diazo chemistry for catalytic stereoselective transformations to further enhance applicability of catalytic metal carbene chemistry in organic synthesis. New catalytic syntheses of multi-functional ¿-keto-a- diazoesters with subsequent catalytic metal carbene transformations provides highly efficient access to more complex carbon frameworks than previously possible through reactions with diazoacetates. We will use active Lewis acidic chiral dirhodium(ll,lll) carboxamidate catalysts to broaden the range of applicable carbon- carbon bond forming transformations. Reactivity and selectivity enhancement through chiral dirhodium(ll,lll) catalysts expands their utilization to Lewis acid catalyzed reactions for which chiral dirhodium(ll,ll) catalysts are ineffective, and initial focus will be given to those transformations for which preliminary results are most promising. We will develop and apply catalytic oxidative methodologies to compounds that are of biological significance. Newly discovered tert-butyl hydroperoxide oxidations catalyzed by dirhodium caprolactamate, based largely on its low oxidation potential and solubilities, offer a unique opportunity to develop a spectrum of oxidative transformations, compatible with water as a solvent, that are not easily achieved by other methods (especially allylic and benzylic oxidations). Applications encompass reactions with steroids, phenolic compounds, unsaturated fatty acids, amines, and other biologically relevant substrates.

本研究计划的目标是设计和开发高选择性和高效的催化剂