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Fluorous

A. Studer, S. Hadida, R. Ferritto, S.Y. Kim, P. Jeyer, P. Wipf, D.P. Curran, Fluorous synthesis — A fluorous-phase strategy for improving separation efficiency in organic synthesis. Science 275 823-826 1997. [Pg.79]

The book also outlines recent developments in synthe (e.g., combinatorial chemishy, solid support chemistry, fluorous chemistry) and the corresponding purification procedures that will provide maiiy of the commercially supplied chrnnical substances in years to come. Additionally, interesting perspective out the future of purification Is jHovided by the autiuxrs, based on their years of experience. [Pg.615]

Chapters 1 and 2 have been reorganised and updated in line with recent developments. A new chapter on the Future of Purification has been added. It outlines developments in syntheses on solid supports, combinatorial chemistry as well as the use of ionic liquids for chemical reactions and reactions in fluorous media. These technologies are becoming increasingly useful and popular so much so that many future commercially available substances will most probably be prepared using these procedures. Consequently, a knowledge of their basic principles will be helpful in many purification methods of the future. [Pg.621]

In comparison with traditional biphasic catalysis using water, fluorous phases, or polar organic solvents, transition metal catalysis in ionic liquids represents a new and advanced way to combine the specific advantages of homogeneous and heterogeneous catalysis. In many applications, the use of a defined transition metal complex immobilized on a ionic liquid support has already shown its unique potential. Many more successful examples - mainly in fine chemical synthesis - can be expected in the future as our loiowledge of ionic liquids and their interactions with transition metal complexes increases. [Pg.253]

Table 6.10 MTO-catalyzed epoxidation of olefins with anhydrous H2O2 or with aqueous H2O2 in fluorous solvents.131... Table 6.10 MTO-catalyzed epoxidation of olefins with anhydrous H2O2 or with aqueous H2O2 in fluorous solvents.131...
Begue and coworkers recently achieved an improvement in this method by performing the epoxidation reaction in hexafluoro-2-propanol [120]. They found that the activity of hydrogen peroxide was significantly increased in this fluorous alcohol, in relation to trifluoroethanol, which allowed for the use of 30% aqueous H202. Interestingly, the nature of the substrate and the choice of additive turned out to have important consequences for the lifetime of the catalyst. Cyclic dis-ubstituted olefins were efficiently epoxidized with 0.1 mol% of MTO and 10 mol%... [Pg.217]

Microwave and fluorous technologies have been combined in the solution phase parallel synthesis of 3-aminoimidazo[l,2-a]pyridines and -pyrazines [63]. The three-component condensation of a perfluorooctane-sulfonyl (Rfs = CgFiy) substituted benzaldehyde by microwave irradiation in a single-mode instrument at 150 °C for 10 min in CH2CI2 - MeOH in the presence of Sc(OTf)3 gave the imidazo-annulated heterocycles that could be purified by fluorous solid phase extraction (Scheme 9). Subsequent Pd-catalyzed cross-coupling reactions of the fluorous sulfonates with arylboronic acids or thiols gave biaryls or aryl sulfides, respectively, albeit it in relatively low yields. [Pg.40]

The use of diamine 27, bearing a fluorous-Boc protecting group, has been used with microwave irradiation in an Ugi/de-Boc/cyclization strategy for the synthesis of benzimidazoles 28 and quinoxalinones 29 [64]. Compared to the original procedures, which take 1-2 days, this approach avoids the use of... [Pg.40]

Scheme 9 Fluorous MCR and subsequent cross-coupling reactions... Scheme 9 Fluorous MCR and subsequent cross-coupling reactions...
Fluorous Synthesis of Biaryl-Subshtuted Proline Analogs. 112... [Pg.79]

Fluorous Mixture Synthesis of Fused-Tricyclic Hydantoins. 114... [Pg.79]

Abstract Current microwave-assisted protocols for reaction on solid-phase and soluble supports are critically reviewed. The compatibility of commercially available polymer supports with the relatively harsh conditions of microwave heating and the possibilities for reaction monitoring are discussed. Instrmnentation available for microwave-assisted solid-phase chemistry is presented. This review also summarizes the recent applications of controlled microwave heating to sohd-phase and SPOT-chemistry, as well as to synthesis on soluble polymers, fluorous phases and functional ionic liquid supports. The presented examples indicate that the combination of microwave dielectric heating with solid- or soluble-polymer supported chemistry techniques provides significant enhancements both at the level of reaction rate and ease of purification compared to conventional procedures. [Pg.80]

Fluorous Synthesis of Biaryl-Substituted Proline Analogs... [Pg.112]

Fig. 30 Microwave-promoted fluorous synthesis of biaryl-subshtuted proline analogs. Reagents and condihons a EtaN, DMF, MW 150 °C, 15 min, 40-75%, closed vials b R""PhB(OH)2, Pd(dppf)Cl2, K3PO4, toluene Acetone H2O, MW 120 °C, 12 min, sealed vial system, 19-79%. R=Me, Et R = Me, 1 - Pr R" = H, 3-MeO R" =Me, Et R""= 4-MeO, 3-Cl, 4-Ac,3,4-diCl,3,4-methylenedioxy... Fig. 30 Microwave-promoted fluorous synthesis of biaryl-subshtuted proline analogs. Reagents and condihons a EtaN, DMF, MW 150 °C, 15 min, 40-75%, closed vials b R""PhB(OH)2, Pd(dppf)Cl2, K3PO4, toluene Acetone H2O, MW 120 °C, 12 min, sealed vial system, 19-79%. R=Me, Et R = Me, 1 - Pr R" = H, 3-MeO R" =Me, Et R""= 4-MeO, 3-Cl, 4-Ac,3,4-diCl,3,4-methylenedioxy...
Fluorous Synthesis of Dihydropteridinones by Microwave-Assisted Cyclative Cleavage... [Pg.113]

Fig. 31 Composition of dihydropteridinone ring system using q clative cleavage in fluorous-phase. Reagents and conditions a EtOAc, MeOH, THE, MW 150 °C, 15 min, sealed vials. Y = C, N, O R = Me, Et, i-Bu, Bn R = H, aromatic or heteroaromatic ring... Fig. 31 Composition of dihydropteridinone ring system using q clative cleavage in fluorous-phase. Reagents and conditions a EtOAc, MeOH, THE, MW 150 °C, 15 min, sealed vials. Y = C, N, O R = Me, Et, i-Bu, Bn R = H, aromatic or heteroaromatic ring...
Fig. 32 Fluorous mixture synthesis of fused-tricyclic hydantoins. Reagents and conditions a Mo(CO)6, DMSO, toluene, MW 150 °C, 35 min, closed system b TFA CH2CI2 (1 1), rt c PhC2H4NH2, PyBOP, i-Pr2EtN, MeOH, CH2CI2 followed by flash chromatography and F-HPLC d i-Pr2EtN, MeOH, MW 140 °C, 40 min, followed by F-SPE... Fig. 32 Fluorous mixture synthesis of fused-tricyclic hydantoins. Reagents and conditions a Mo(CO)6, DMSO, toluene, MW 150 °C, 35 min, closed system b TFA CH2CI2 (1 1), rt c PhC2H4NH2, PyBOP, i-Pr2EtN, MeOH, CH2CI2 followed by flash chromatography and F-HPLC d i-Pr2EtN, MeOH, MW 140 °C, 40 min, followed by F-SPE...
Fig. 33 Microwave-assisted fluorous Ugi condensations. Reagents and conditions a MeOH, MW 100°C, 10-20 min b TFA-THF, MW 100 °C, 10-20 min. R = Ph, furyl, 3-Me-pyridil, i-Bu, MeSC2H4, PhC2H4 R = t-Bu, cylohexyl. Bn or Bu, m-xylU... Fig. 33 Microwave-assisted fluorous Ugi condensations. Reagents and conditions a MeOH, MW 100°C, 10-20 min b TFA-THF, MW 100 °C, 10-20 min. R = Ph, furyl, 3-Me-pyridil, i-Bu, MeSC2H4, PhC2H4 R = t-Bu, cylohexyl. Bn or Bu, m-xylU...
By replacing insoluble cross-linked resins with soluble polymer supports, the well-estabhshed reaction conditions of classical organic chemistry can be more readily apphed, while still fadhtating product purification. However, soluble supports suffer from the hmitation of low loading capacity. The recently introduced fluorous synthesis methodology overcomes many of the drawbacks of both the insoluble beads and the soluble polymers, but the high cost of perfluoroalkane solvents, hmitation in solvent selection, and the need for specialized reagents may hmit its apphcations. [Pg.116]

Fig. 41 Representative example of microwave-assisted Suzuki couplings in fluorous phase. Reagents and conditions [Pd(dppf)Cl2], K2CO3, toluene/acetone/H20, MW 130°C, 10 min, closed system, 78%... Fig. 41 Representative example of microwave-assisted Suzuki couplings in fluorous phase. Reagents and conditions [Pd(dppf)Cl2], K2CO3, toluene/acetone/H20, MW 130°C, 10 min, closed system, 78%...
Gladysz JA, Curran DP, Horvath IT (eds) (2004) Handbook of Fluorous Chemistry. WUey, Weinheim... [Pg.152]


See other pages where Fluorous is mentioned: [Pg.72]    [Pg.77]    [Pg.77]    [Pg.79]    [Pg.620]    [Pg.2]    [Pg.69]    [Pg.181]    [Pg.260]    [Pg.281]    [Pg.329]    [Pg.32]    [Pg.41]    [Pg.41]    [Pg.79]    [Pg.79]    [Pg.79]    [Pg.87]    [Pg.112]    [Pg.112]    [Pg.112]    [Pg.113]    [Pg.114]    [Pg.115]    [Pg.123]    [Pg.123]    [Pg.131]   
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A Green Chemistry Strategy Fluorous Catalysis

Accelerated Chemistry Microwave, Sonochemical, and Fluorous Phase Techniques

Acid fluorous tagged

Aggregate, fluorous

Aldehydes fluorous tagged

Allyltin fluorous

Alternative fluorous solvents

Aryl fluorous-phase synthesis

Automated Oligosaccharide Synthesis Using Fluorous Tags

BINAP fluorous

BINOLs fluorous

Basics of Fluorous Chemistry

Bidentate ligands fluorous-tagged

Biocatalysis fluorous solvents

Biphasic fluorous media

Boronates fluorous

Catalysis fluorous

Catalyst fluorous

Catalyst fluorous biphasic

Catalyst scavenger, fluorous

Catalysts fluorous biphasic catalysis concept

Catalysts separation, fluorous

Catalysts separation, fluorous biphasic

Chromatography fluorous

Condensation fluorous-tagged

Designing fluorous catalysts

Diels-Alder reactions fluorous

Dihydropteridinones, fluorous synthesis

Dihydropteridinones, fluorous synthesis cyclative cleavage

Distannoxanes, fluorous

Electron-withdrawing fluorous ligands

Enantioselective Fluorous Catalysis

Enhanced High-Speed Fluorous Synthesis Zhang

Epoxidation fluorous catalysis

Esterification of alcohol with acetic anhydride using a fluorous scandium catalyst

Extraction fluorous solvents

Ferrocenes, fluorous

Fluorinated fluorous mixture synthesis

Fluorination fluorous interactions

Fluorous Applications in High-Throughput

Fluorous BINOL

Fluorous Biphase Solvents

Fluorous Catalysts and Reagents

Fluorous Combinatorial Chemistry

Fluorous Concepts in Combinatorial Chemistry

Fluorous Corey—Kim reaction

Fluorous DEAD

Fluorous DMSO

Fluorous Ether

Fluorous Grubbs’ catalysts

Fluorous HPLC separation

Fluorous Heck couplings

Fluorous IBX

Fluorous Liquids

Fluorous Materials Chemistry

Fluorous Mukaiyama reagent

Fluorous Palladacycle Catalysts

Fluorous Phase Techniques

Fluorous Phase-Separation Techniques in Catalysis

Fluorous Protecting Groups

Fluorous Salen

Fluorous Schiff base

Fluorous Stille reactions

Fluorous Subject

Fluorous Suzuki couplings

Fluorous Swern oxidation

Fluorous Synthesis and Combinatorial Chemistry

Fluorous Techniques Progress in Reaction-Processing and Purification

Fluorous Ugi reactions

Fluorous Wilkinson Catalyst

Fluorous acid and base catalysts

Fluorous aerobic oxidations

Fluorous alcohol

Fluorous alkylstannanes

Fluorous allylic oxidation

Fluorous allylstannanes

Fluorous amine protection

Fluorous aminosulfonamide-catalyzed aldol

Fluorous azide

Fluorous benzotrifluoride

Fluorous benzyl group

Fluorous benzyl protective group

Fluorous biphase

Fluorous biphase catalysis

Fluorous biphase system

Fluorous biphase systems, FBS

Fluorous biphase techniques

Fluorous biphasic

Fluorous biphasic catalysis

Fluorous biphasic catalysis catalysts

Fluorous biphasic catalysis concept

Fluorous biphasic catalysis ligands

Fluorous biphasic catalysis reaction

Fluorous biphasic concept

Fluorous biphasic condition

Fluorous biphasic solvent systems

Fluorous biphasic solvents

Fluorous biphasic systems

Fluorous bipyridine

Fluorous carbene complex

Fluorous carbodiimide

Fluorous carboxylic acid protecting group

Fluorous catalytic acetalization reaction

Fluorous catalytic oxidation reaction

Fluorous chemistry

Fluorous chiral

Fluorous chiral diamine

Fluorous complex

Fluorous compounds

Fluorous compounds Catalysts

Fluorous compounds Reagents

Fluorous dendrimer

Fluorous dienophile

Fluorous effects

Fluorous extraction

Fluorous extraction, Swern oxidation

Fluorous fluids

Fluorous fluorine content differences

Fluorous groups

Fluorous heavy

Fluorous hydride

Fluorous hydroboration

Fluorous hydroformylation

Fluorous hydrogenation

Fluorous imidazolium salt

Fluorous immobilization

Fluorous interactions

Fluorous intermediates synthesis

Fluorous isolation tags

Fluorous label

Fluorous layer

Fluorous ligand recycling

Fluorous ligands

Fluorous ligands, examples

Fluorous light

Fluorous media

Fluorous metallic catalysis

Fluorous metallic catalysis catalysts

Fluorous metallic catalysis complexes

Fluorous mixture synthesis

Fluorous mixture synthesis examples

Fluorous olefin oxidation

Fluorous oxidation

Fluorous palladacycles

Fluorous palladium complexes

Fluorous partition coefficients

Fluorous phase

Fluorous phase chemistry

Fluorous phase chemistry microwave-enhanced

Fluorous phase organic synthesis

Fluorous phase reactions

Fluorous phase separation

Fluorous phase separation techniques

Fluorous phosphane ligand

Fluorous phosphate protection

Fluorous phosphine ligand

Fluorous polymerizations

Fluorous pony-tail, catalysts with

Fluorous ponytails

Fluorous porphyrin

Fluorous protective groups

Fluorous protective groups alcohols

Fluorous quasi-racemic synthesis

Fluorous reactions

Fluorous reagents and ligands

Fluorous recycling

Fluorous reverse phase silica gel

Fluorous reversed-phase silica gel

Fluorous rhodium complexes

Fluorous separation

Fluorous separation method

Fluorous silyl group

Fluorous small-molecule microarrays

Fluorous solid

Fluorous solid catalyst

Fluorous solid-phase extraction

Fluorous solid-phase extraction F-SPE)

Fluorous soluble

Fluorous solvent miscibilities

Fluorous solvents Subject

Fluorous solvents epoxidation

Fluorous solvents miscibility

Fluorous solvents partition coefficients

Fluorous solvents solubility

Fluorous solvents triphasic reactions

Fluorous solvents, Diels—Alder

Fluorous solvents, Diels—Alder reactions with

Fluorous solvents, examples

Fluorous solvents, phase separation, effect

Fluorous substituent

Fluorous substrates

Fluorous supports

Fluorous switching techniques

Fluorous synthesi

Fluorous synthesis

Fluorous synthesis microwave-assisted

Fluorous synthesis, high-speed

Fluorous systems, Heck reactions

Fluorous tag

Fluorous tagging strategy

Fluorous tails

Fluorous techniques

Fluorous technology

Fluorous tin azide

Fluorous tin reagents

Fluorous triphasic reaction

Fluorous, hydroformylation reaction

Fluorous-Tagged Scavengers

Fluorous-Tagged Thiols

Fluorous-based carbohydrate

Fluorous-based carbohydrate microarrays

Fluorous-phase conditions

Fluorous-phase label

Fluorous-phase synthesis

Fluorous-tagged

H2O2 in Fluorous Phase and Related Reactions

Heavy fluorous compounds

Heavy fluorous reagents

Heck vinylations, fluorous

High-throughput chemistry fluorous applications

Hydantoins fluorous-phase synthesis

Hydantoins fused-tricyclic, fluorous mixture

Hydroformylation in fluorous solvents

Hydrogen fluorous phase

Hydrogenation in fluorous solvents

I 3 Fluorous Chemistry

Isocyanate fluorous-tagged

Isoxazolines, fluorous-tagged

Lewis acids fluorous systems

Light Fluorous-Tag-Assisted Synthesis of Oligosaccharides

Light fluorous catalyst

Light fluorous compounds

Light fluorous protecting groups

Light fluorous reagent

Light fluorous-tag-assisted synthesis

Linker fluorous

Mappicine library fluorous mixture synthesis

Microwave-Enhanced Fluorous Chemistry

Mitsunobu reaction using fluorous reagents

Multicomponent fluorous-phase

Natural products fluorous mixture synthesis

Olefin Metathesis in Fluorous Media

Olefin fluorous biphasic system

Organocatalysts fluorous catalyst

Other fluorous reagents

Outlook for Fluorous Solvents and Ionic Liquids

Phosphines fluorous

Phosphinite fluorous

Phosphite, fluorous

Phosphonites fluorous

Polarity fluorous solvents

Ponytails fluorous ligands

Process Synthesis for the Fluorous Biphasic Hydroformylation of 1-Octene

Product fluorous biphase concept

Proline analogs, biaryl-substituted fluorous synthesis

Protecting fluorous

Pyrrolidine fluorous sulfonamide

Pyrrolidines fluorous

Pyrrolidines fluorous sulfonamide

Radical fluorous phase

Reaction fluorous solvent

Reactions in Fluorous Media

Reagents fluorous

Recycling fluorous catalysts

Scavenger fluorous

Separation fluorous biphasic

Silica reversed-phase, fluorous

Silica, fluorous

Solid-phase extractions with fluorous silica gel

Solid-phase/fluorous synthesis

Solvent fluorous

Solvents, acidic fluorous

Stille fluorous

Sulfoxides fluorous

Super fluorous

Supercritical fluorous catalysis

Suzuki coupling microwave-assisted fluorous phase

Suzuki fluorous

Suzuki reactions fluorous

TEMPO catalyst, fluorous

Tagging fluorous

Thiourea catalysts fluorous

Tributyltin fluorous

Triphenylphosphine fluorous reagent

Vinylation, fluorous

Wilkinson fluorous

Wilkinson fluorous analogue

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