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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.

该研究计划的目标是设计和开发高选择性和高效的催化剂，生物学相关化合物的合成方法。调查将建立在我们最新的发现了氨甲酰二铑的独特催化用途。在其应用程序中的突破，化学氧化和作为手性刘易斯酸已经证明了这些化合物的极大增强的通用性。催化剂将进一步探索。这些催化剂的固定的立体限定的几何形状提供了进入重氮乙酸盐的金属卡宾反应中的高度对映体富集的产物，以及它们的低氧化电位，还提供了高选择性刘易斯酸催化反应的能力，有效的化学氧化。在所有目标中，我们寻求高流动性和高选择性。在这在资助期内，我们将解决手性二铑羧酰胺化物用于金属卡宾转化的局限性- 通过新的方法，其初步结果表明目标将实现。我们将开发用于催化立体选择性转化的重氮化学，以进一步增强有机合成中的催化金属卡宾化学。多功能戊酮-α-酮的催化合成新方法重氮酯与随后的催化金属卡宾转化提供了高效的获得更多通过与重氮乙酸酯的反应，比以前可能的更复杂的碳框架。我们将使用活性刘易斯酸性手性二铑（II，III）甲酰胺化物催化剂，以拓宽可应用的碳- 碳键形成转变。手性铑（II，III）催化剂的反应性和选择性提高催化剂将它们的应用扩展到刘易斯酸催化的反应，对于该反应，手性铑（II，II）催化剂是无效的，最初的重点将放在那些初步成果最重要的转型上。很有希望我们将开发和应用催化氧化方法学的化合物，是生物意义新发现的己内酰胺二铑催化的叔丁基过氧化氢氧化反应，主要基于其低氧化电位和溶解度，提供了一个独特的机会，氧化转化，与水作为溶剂相容，这是不容易实现的其他方法（特别是烯丙基和苄基氧化）。应用包括与类固醇的反应，酚类化合物、不饱和脂肪酸、胺和其它生物学相关底物。