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：
8136565
负责人：
Michael PATRICK Doyle
金额：
$ 29.4万
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/8136565
关键词：
3-hydroxybutanal Acetates Acetone Acidity Acids Age Alcohols Aldehydes Alder plant Alkenes Amides Amines Area Aromatic Amines Aziridines BINAP BINOL Benzodiazepines Biological Biological Factors Book Chapters 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 Effectiveness 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 Lactams Lactones Lead Ligands Link Manganese Manuscripts Mediating Metals Methodology Methods Modeling Modification Nitrogen Organic Synthesis Outcome Oxonia Active Oxygen Palladium Pathway interactions Phenols Physical condensation Polymers Positioning Attribute Potassium Preparation Procedures Process Proline Publications Publishing Pyrazoles Pyrroles Pyrrolidines Quinine Reaction Recovery Relative (related person)Reporting Research Research Peer Review Resort Rhodium Role Route Ruthenium Scandium Scheme Site Solubility Solvents Steroids Sulfonamides System Temperature Thermodynamics Titania 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 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.

该研究计划的目的是设计和开发高度选择性，高效的催化过程，以合成生物学相关化合物。调查将基于我们最新发现，并使用dirhodium羧酰胺剂的独特催化用途。在化学氧化的应用中的突破和手性刘易斯酸已经显示出这些催化剂的多功能性大大增强，将进一步探索。这些催化剂的固定立体置换几何形状可访问重生乙酸盐的金属碳烯反应中高度对映射的产物，并及其低氧化潜力，还为高度选择性的路易斯酸催化的反应和有效的化学氧化提供了能力。在所有目标中，我们都寻求高尚额的数字和高选择性。在这个资金期间，我们将通过新的过程来解决金属碳纤维转化的手性dirhodium羧酰胺剂的局限性，这些过程表明将实现目标。我们将开发重氮化学，用于催化立体选择转化，以进一步增强催化金属碳化学在有机合成中的适用性。多功能B酮-A-的新催化合成随后的催化金属碳转化的重氮植物比以前通过与重生乙酸盐的反应相比，可以高效地进入更复杂的碳框架。我们将使用活跃的路易斯酸性手性dirhodium（LL，LLL）羧化催化剂来扩大适用的碳碳键形成变换的范围。通过手性dirhodium（LL，LLL）催化剂的反应性和选择性提高，将其利用扩大到刘易斯酸催化反应，手性dirhodium（LL，LL）催化剂无效，最初的焦点将对这些初步结果最初的焦点，以实现这些反应。有希望的。我们将开发并应用催化氧化方法，以具有生物学意义的化合物。新发现的丁烷氢过氧化物氧化是由Dirhodium caprolactamate催化的，主要基于其低氧化潜力和溶解度，提供了一个独特的机会，可以开发出与水作为或者相兼容的氧化转化，这些氧化转化与某种方法相兼容，尤其是其他方法（尤其是其他方法）（尤其是benz yelghyalic和Benz yebyalic和Benzy）。应用包括与类固醇，酚类化合物，不饱和脂肪酸，胺和其他与生物学相关的底物的反应。