均相催化

內(nèi)容概要

過(guò)渡金屬化合物均相催化領(lǐng)城近年來(lái)發(fā)展非常迅速，工業(yè)界、學(xué)術(shù)界紛紛報(bào)道發(fā)現(xiàn)了眾多的奇妙催化劑。本書(shū)基于作者在教學(xué)及工業(yè)實(shí)踐方面廣泛的經(jīng)驗(yàn)，探討了許多新的和舊的重要反應(yīng)。每章均以基礎(chǔ)知識(shí)開(kāi)始，以最新的內(nèi)容結(jié)束。本書(shū)側(cè)重于概念，但也列舉了許多實(shí)驗(yàn)室合成有機(jī)化學(xué)品的關(guān)鍵丁業(yè)流程和應(yīng)用流程。全書(shū)涵蓋精細(xì)化學(xué)品，大宗化學(xué)品，聚合物，高技術(shù)聚合物，藥品，也包括重要的技巧和反應(yīng)類型等。同時(shí)還介紹了一些反應(yīng)過(guò)程方案、環(huán)境問(wèn)題和安全問(wèn)題。 本書(shū)可供催化專業(yè)高年級(jí)本科生、研究生以及研究人員參考使用。

書(shū)籍目錄

PrefaceAcknowledgements1.  INTRODUCTION  1.1  CATALYSIS  1.2  HOMOGENEOUS CATALYSIS  1.3  HISTORICAL NOTES ON HOMOGENEOUS CATALYSIS  1.4  CHARACTERISATION OF THE CATALYST  1.5  LIGAND EFFECTS    1.5.1  Phosphines and phosphites: electronic effects    1.5.2  Phosphines and phosphites: steric effects    1.5.3  Linear Free Energy Relationships    1.5.4  Phosphines and phosphites: bite angle effects  1.6  LIGANDS ACCORDING TO DONOR ATOMS    1.6.1  Anionic and neutral hydrocarbyl groups    1.6.2  Alkoxy and imido groups as anionic ligands    1.6.3  Amines, imines, oxazolines and related ligands    1.6.4  Phosphines, phosphites, phosphorus amides, phospholes and related ligands    1.6.5  Carbenes, carbon monoxide    1.6.6  Common anions2.  ELEMENTARY STEPS  2.1  CREATION OF A "VACANT" SITE AND CO-ORDINATION OF THE SUBSTRATE  2.2  INSERTION VERSUS MIGRATION  2.3  β-ELIMINATION AND DE-INSERTION  2.4  OXIDATIVE ADDITION  2.5  REDUCTIVE ELIMINATION  2.6  α-ELIMINATION REACTIONS  2.7  CYCLOADDITION REACTIONS INVOLVING A METAL  2.8  ACTIVATION OF A  SUBSTRATE TOWARD NUCLEOPHILIC  ATTACK    2.8.1  Alkenes    2.8.2  Alkynes    2.8.3  Carbon monoxide    2.8.4  Other substrates  2.9  a-BOND METATHESIS  2.10  DIHYDROGEN ACTIVATION  2.11  ACTIVATION BY LEWIS ACIDS    2.11.1  Diels-Alder additions    2.11.2  Epoxidation    2.11.3  Ester condensation  2.12  CARBON-TO-PHOSPHORUS BOND BREAKING  2.13  CARBON-TO-SULFUR BOND BREAKING  2.14  RADICAL REACTIONS3. KINETICS  3.1  INTRODUCTION  3.2  TWO-STEP REACTION SCHEME  3.3  SIMPLIFICATIONS OF THE RATE EQUATION AND THE RATEDETERMINING STEP  3.4  DETERMINING THE SELECTIVITY  3.5  COLLECTION OF RATE DATA  3.6  IRREGULARITIES IN CATALYSIS4.  HYDROGENATION  4.1  WILKINSON'S CATALYST  4.2  ASYMMETRIC HYDROGENATION    4.2.1  Introduction    4.2.2  Cinnamic acid derivatives    4.2.3  Chloride versus weakly coordinating anions; alkylphosphines versus arylphosphines    4.2.4  Incubation times  4.3  OVERVIEW OF CHIRAL BIDENTATE LIGANDS    4.3.1  DUPHOS    4.3.2  BINAP catalysis    4.3.3  Chiral ferrocene based ligands  4.4  MONODENTATE LIGANDS  4.5  NON-LINEAR EFFECTS  4.6  HYDROGEN TRANSFER5.  ISOMERISATION  5.1  HYDROGEN SHIFTS  5.2  ASYMMETRIC ISOMERISATION  5.3  OXYGEN SHIFTS6.  CARBONYLATION OF METHANOL AND METHYL ACETATE  6.1  ACETIC ACID  6.2  PROCESS SCHEME MONSANTO PROCESS  6.3  ACETIC ANHYDRIDE  6.4  OTHER SYSTEMS    6.4.1  Higher alcohols    6.4.2  Phosphine-modified rhodium catalysts    6.4.3  Other metals7.  COBALT CATALYSED HYDROFORMYLATION  7.1  INTRODUCTION  7.2  THERMODYNAMICS  7.3  COBALT CATALYSED PROCESSES  7.4  COBALT CATALYSED PROCESSES FOR HIGHER ALKENES  7.5  KUHLMANN COBALT HYDROFORMYLATION PROCESS  7.6  PHOSPHINE MODIFIED COBALT CATALYSTS: THE SHELL PROCESS  7.7  COBALT CARBONYL PHOSPHINE COMPLEXES    7.7.1  Carbonyl species    7.7.2  Phosphine derivatives8.  RHODIUM CATALYSED HYDROFORMYLATION  8.1  INTRODUCTION  8.2  TRIPHENYLPHOSPHINE AS THE LIGAND   8.2.1  The mechanism    8.2.2  Ligand effects and kinetics    8.2.3  Regioselectivity    8.2.4  Process description, rhodium-tpp    8.2.5  Two-phase process, tppts: Ruhrchemie/Rhone-Poulenc    8.2.6  One-phase catalysis, two-phase separation  8.3  DIPHOSPHINES AS LIGANDS    8.3.1  Xantphos ligands: tuneable bite angles  8.4  PHOSPHITES AS LIGANDS    8.4.1  Electronic effects    8.4.2  Phosphites: steric effects  8.5  DIPHOSPHITES  8.6  ASYMMETRIC HYDROFORMYLATION    8.6.1  Rhodium catalysts: diphosphites    8.6.2  Rhodium catalysts: phosphine-phosphite ligands9.  ALKENE OLIGOMERISATION  9.1  INTRODUCTION  9.2  SHELL-HIGHER-OLEFINS-PROCESS    9.2.1  Oligomerisation    9.2.2  Separation    9.2.3  Purification, isomerisation, and metathesis    9.2.4  New catalysts  9.3  ETHENE TRIMERISATION  9.4  OTHER ALKENE OLIGOMERISATION REACTIONS10.  PROPENE POLYMERISATION  10.1  INTRODUCTION TO POLYMER CHEMISTRY    10.1.1  Introduction to Ziegler Natta polymerisation    10.1.2  History of homogeneous catalysts  10.2  MECHANISTIC INVESTIGATIONS    10.2.1  Chain-end control: syndiotactic polymers    10.2.2  Chain-end control: isotactic polymers  10.3  ANALYSIS BY13C NMR SPECTROSCOPY    10.3.1  Introduction    10.3.2  Chain-end control    10.3.3  Site control mechanism  10.4  THE DEVELOPMENT OF METALLOCENE CATALYSTS    10.4.1  Site control: isotactic polymers    10.4.2  Site control: syndiotactic polymers    10.4.3  Double stereoselection: chain-end and site control  10.5  AGOSTIC INTERACTIONS  10.6  THE EFFECT OF DIHYDROGEN  10.7  FURTHER WORK USING PROPENE AND OTHER ALKENES  10.8  NON-METALLOCENE ETM CATALYSTS  10.9  LATE TRANSITION METAL CATALYSTS11.  HYDROCYANATION OF ALKENES  11.1  THE ADIPONITRILE PROCESS  11.2  LIGAND EFFECTS 12.  PALLADIUM CATALYSED CARBONYLATIONS OF ALKENES  12.1  INTRODUCTION  12.2  POLYKETONE    12.2.1  Background and history    12.2.2  Elementary steps: initiation    12.2.3  Elementary steps: migration reactions    12.2.4  Elementary steps: chain termination, chain transfer    12.2.5  Elementary steps: ester formation as chain termination  12.3  LIGAND EFFECTS ON CHAIN LENGTH    12.3.1  Polymers    12.3.2  Ligand effects on chain length: Propanoate    12.3.3  Ligand effects on chain length: Oligomers  12.4  ETHENE/PROPENE/CO TERPOLYMERS  12.5  STEREOSELECTIVE STYRENE/CO COPOLYMERS13.  PALLADIUM CATALYSED CROSS-COUPLING REACTIONS  13.1  INTRODUCTION  13.2  ALLYLIC ALKYLATION  13.3  HECK REACTION  13.4  CROSS-COUPLING REACTION  13.5  HETEROATOM-CARBON BOND FORMATION  13.6  SUZUKI REACTION14.  EPOXIDATION  14.1  ETHENE AND PROPENE OXIDE  14.2  ASYMMETRIC EPOXIDATION    14.2.1  Introduction    14.2.2  Katsuki-Sharpless asymmetric epoxidation    14.2.3  The Jacobsen asymmetric epoxidation  14.3  ASYMMETRIC  HYDROXYLATION  OF  ALKENES  WITH  OSMIUM TETROXIDE    14.3.1  Stoichiometric reactions    14.3.2  Catalytic reactions  14.4  JACOBSEN ASYMMETRIC RING-OPENING OF EPOXIDES  14.5  EPOXIDATIONS WITH DIOXYGEN 15. OXIDATION WITH DIOXYGEN  15.1  INTRODUCTION  15.2  THE WACKIER REACTION  15.3  WACKIER TYPE REACTIONS  15.4  TEREPHTHALIC ACID  15.5  PPO 16.  ALKENE METATHESIS  16.1  INTRODUCTION  16.2  THE MECHANISM  16.3  REACTION OVERVIEW  16.4  WELL-CHARACTERISED  TUNGSTEN  AND  MOLYBDENUM CATALYSTS  16.5  RUTHENIUM CATALYSTS  16.6  STEREOCHEMISTRY  16.7  CATALYST DECOMPOSITION  16.8  ALKYNES  16.9  INDUSTRIAL APPLICATIONS17.  ENANTIOSELECTIVE CYCLOPROPANATION  17.1  INTRODUCTION  17.2  COPPER CATALYSTS  17.3  RHODIUM CATALYSTS    17.3.1  Introduction    17.3.2  Examples of rhodium catalysts18. HYDROSILYLATION  18.1  INTRODUCTION  18.2  PLATINUM CATALYSTS  18.3  ASYMMETRIC PALLADIUM CATALYSTS  18.4  RHODIUM CATALYSTS FOR ASYMMETRIC KETONE REDUCTION19.  C-H FUNCTIONALISATION  19.1  INTRODUCTION  19.2  ELECTRON-RICH METALS  19.3  HYDROGEN TRANSFER REACTIONS OF ALKANES  19.4  BORYLATION OF ALKANES  19.5  THE MURAI REACTION  19.6  CATALYTIC a-BOND METATHESIS  19.7  ELECTROPHILIC CATALYSTSSUBJECT INDEX

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