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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：
7928258
负责人：
Michael PATRICK Doyle
金额：
$ 29.7万
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/7928258
关键词：
3-hydroxybutanal Acetates Acetone Acidity Acids Age Alcohols Aldehydes Alder plant Alkenes Amides Amines Area Aromatic Amines Aziridines Benzodiazepines Biological Biological Factors Books Bromides Carbon Carbonates Catalysis Characteristics Chemicals Chemistry Chromium Cobalt Collaborations Complex 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 Exclusion Free Energy Funding Goals Grant Heterocyclic Compounds High Pressure Liquid Chromatography Hydrogen Hydrogen Bonding 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 Organic Synthesis Outcome Oxygen Palladium Pathway interactions Phenols Physical condensation Polymers Positioning Attribute Potassium Preparation Process Proline Publishing Pyrazoles Pyrroles Pyrrolidines Quinine Reaction Recovery Relative (related person)Reporting Research Research Peer Review Resort Rhodium Role Route Ruthenium Scandium Scheme Site Slide Solubility Solvents Steroids Sulfonamides System Temperature Thermodynamics Titanium Toluene Transfer RNA United States National Institutes of Health Unsaturated Fatty Acids Variant Vertebral column Water alkyl group analog azetidinone base carbene carbonyl compound carboxylate catalyst coping cycloaddition cyclopropane decane deprotonation design diazo compound dirhodium tetraacetate enol hydronium ion inhibitor/antagonist insight interest novel oxidation peroxidation pi bond prevent programs pyridine pyrrolidine pyrroline racemization 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 transformations 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 B-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用于合成生物相关化合物的高选择性和高效催化工艺。调查将建立在我们的最新发现与独特的催化用途的dirhodium carboxamidates。它们在化学氧化和作为手性刘易斯酸的应用中的突破已经证明了这些催化剂的极大增强的通用性，这将被进一步探索。这些催化剂的固定的立体限定的几何形状提供了在重氮乙酸盐的金属卡宾反应中获得高度对映体富集的产物的途径，并且与它们的低氧化电位一起，还提供了用于高度选择性的刘易斯酸催化反应和有效的化学氧化的能力。在所有目标中，我们寻求高流动性和高选择性。在此资助期间，我们将解决手性二铑羧酰胺金属卡宾转换的限制，通过新的工艺，初步结果表明，目标将实现。我们将发展重氮化学用于催化立体选择性转化，以进一步提高催化金属卡宾化学在有机合成中的应用。多功能B-酮基-a- 重氮酯与随后的催化金属卡宾转化提供了比先前通过与重氮乙酸酯反应可能获得的更复杂的碳骨架的高效途径。我们将使用活性刘易斯酸性手性二铑（II，III）甲酰胺催化剂来拓宽适用的碳-碳键形成转化的范围。通过手性二铑（II，III）催化剂的反应性和选择性增强将它们的应用扩展到手性二铑（II，III）催化剂无效的刘易斯酸催化的反应，并且初始焦点将给予那些初步结果最多的转化。很有希望我们将开发和应用催化氧化方法对具有生物学意义的化合物。新发现的叔丁基过氧化氢的氧化催化的己内酰胺二铑，主要是基于其低氧化电位和溶解度，提供了一个独特的机会，开发一系列的氧化转化，兼容水作为溶剂，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、酚类化合物、不饱和脂肪酸、胺和其他生物相关底物的反应。