g Bh Evul Can Catalytic Reaction Guide

8/10/2019 g Bh Evul Can Catalytic Reaction Guide

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HETEROGENEOUS REACTION CHEMISTRY

CONTENTS

0 HETEROGENEOUS POWDERED CATALYSTS

1 CHOICE OF METAL

2 CHOICE OF SUPPORT

3 MASS TRANSPORT AND REACTOR DESIGN

4 CATALYST DESIGN

5 CATALYST SEPARATION, FILTRATION

6 PROCESS ECONOMICS


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VULCAN Catalytic Reaction GuideChemistry Reactions

1. Hydrogenation 1-55

1.1 C-C Multiple Bonds 1-7

1.2 Aromatic Ring Compounds 8-14

1.3 Carbonyl Compounds 15-25

1.4 Nitro and Nitroso Compounds 28-351.5 Halonitroaromatics 36

1.6 Reductive Alkylation's 37 & 38

1.7 Imines 39-41

1.8 Nitriles 42-47

1.9 Oximes 48-49

1.10 Hydrogenolysis 50-54

1.11 Other 55

2. Dehydrogenation 56-60

3. Hydrofo rmylation 61& 62

4. Carbonylation 63-68

5. Decarbonylation 69

6. Hydrosilylation 70 & 71

7. Cross Coupling 72-96

Catalytic Reaction Guide: (106) Heterogeneous Reaction Mechanisms


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0 HETEROGENEOUS POWDERED CATALYSTS

Supported precious metal catalysts are used for a variety of reactionsincluding hydrogenation, dehydrogenation, hydrogenolysis, oxidation,disproportionation and isomerization. Many important organictransformations are completed via catalytic hydrogenation. A large numberof these reactions are carried out in the liquid phase, using batch typeslurry processes and a supported heterogeneous platinum group metal

catalyst. Platinum group metal catalysts will reduce most organicfunctional groups.

The selection of a catalyst or catalyst system for a new catalytic processrequires many important technical and economic considerations. Theprocess of selecting a precious metal catalyst can be broken down intocomponents. Key catalyst properties are high activity, high selectivity, highrecycle capability and filterability. Important process components include

choice of catalytic metal, choice of support, reactor design, heat and masstransport, catalyst design, catalyst separation, and spent catalyst recoveryand refining.

1 CHOICE OF METAL

Catalyst performance is determined mainly by the precious metalcomponent. A metal is chosen based both on its ability to complete thedesired reaction and its inability to complete an unwanted reaction.


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2 CHOICE OF SUPPORT

In general, a catalyst support should allow for a high degree of metaldispersion. The choice of support is largely determined by the nature ofthe reaction system. A support should be stable under reaction andregeneration conditions, and not adversely interact with solvent, reactantsor reaction products. Common powdered supports include activatedcarbon, alumina, silica, silica-alumina, carbon black, TiO2, ZrO2, CaCO3,and BaSO4. The majority of precious metal catalysts are supported on

either carbon or alumina. Information on common powdered supports issummarized on Page 5.

Figure 1. The Effect of Catalyst Support on Platinum Dispersion


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Support porosity affects metal dispersion and distribution, metal sintering

resistance, and intraparticle diffusion of reactants, products and poisons.Smaller support particle size increases catalytic activity but decreasesfilterability. A support should have desirable mechanical properties,attrition resistance and hardness. An attrition resistant support allows formultiple catalyst recycling and rapid filtration. Support impurities maydeactivate the metal and enhance catalyst selectivity.

The concentration of precious metal deposited on a support is typically

between 1 and 10 weight percent. Practical metal concentration limits arebetween 0.1 and 20 weight percent for activated carbon, and between 0.1and 5 weight percent for alumina. Relative catalyst activity will generallyincrease with decreasing metal concentration at constant metal loading.

3 MASS TRANSPORT AND REACTOR DESIGN

Liquid phase hydrogenations employing heterogeneous catalysts aremultiple phase (gas-liquid-solid) systems containing concentration andtemperature gradients. In order to obtain a true measure of catalyticperformance, heat transfer resistances and mass transfer resistancesneed to be understood and minimized. Mass transfer effects can alterreaction times, reaction selectivity, and product yields. The intrinsic rate ofa chemical reaction can be totally obscured when a reaction is masstransport limited. For reaction to take place in a multi-phase system,the following steps must occur: 1) transport of the gaseous reactant into


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Figure 2. Concentration Gradients in Gas/Liquid/Solid Catalytic system

of the dissolved gaseous reactant through the bulk liquid to the surface ofa catalyst particle 3) transport of the dissolved substrate through the liquid


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A reaction controlled by pore diffusion-chemical reaction, i.e. the rate of

reactant diffusion and chemical reaction within the catalyst particle, will beinfluenced mainly by temperature, reactant concentration, percent metalon the support, number and location of active catalytic sites, catalystparticle size distribution and pore structure. To evaluate and rank catalystsin order of intrinsic catalytic activity, it is necessary to operate underconditions where mass transfer is not rate limiting. A reactor used forliquid phase hydrogenations should provide for good gas-liquid and liquid-solid mass transport, heat transport, and uniformly suspend the solid

catalyst.

4 CATALYST DESIGN

The size of the deposited precious metal particulates and their location onthe support material affect the properties and performance of aheterogeneous catalyst. Increased metal dispersion and decreased metalparticle size generally result in increased catalyst activity. Metal location

and metal dispersion can be controlled during catalyst manufacture. Metalparticulates can be deposited preferentially at the exterior surface of thesupport to give what is termed an eggshell or surface-loaded catalyst.Catalysts with metal particulates evenly dispersed throughout the supportstructure are referred to as having a standard or uniform metaldistribution (Figure 3).

Figure 3. Schematic of Metal Location


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particulates can be deposited preferentially at the exterior surface of thesupport to give what is termed an eggshell or surface-loaded catalyst.Catalysts with metal particulates evenly dispersed throughout the supportstructure are referred to as having a standard or uniform metaldistribution (Figure 3).

Catalysts are designed with different metal locations for reactions whichtake place under different conditions of pressure and temperature.

Hydrogenation reactions are generally first order with respect to hydrogen.As such, standard catalysts with increased metal dispersions typicallyexhibit greater relative activity at high hydrogen pressures. Eggshellcatalysts exhibit higher relative activity at low hydrogen pressures.Hydrogenation of large molecules is generally carried out using eggshellcatalysts. Variation of metal location can also be used to alter catalystselectivity.

Location of catalytic metal deep into the pore structure of the support maylead to significant reactant pore diffusion limitations. Such catalysts,however, are generally more poison resistant because catalyst poisonsare typically of high molecular weight, and unlike smaller reactantmolecules, are unable to penetrate into the catalyst pore structure todeactivate the catalytic metal.

Deposited metal may be either in a reduced or unreduced form.

Unreduced catalysts are readily reduced under the conditions of thecatalytic hydrogenation itself, and are often more active than reduced


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5 CATALYST SEPARATION, FILTRATION

A good powdered catalyst should be easy to separate from the reactionmixture and final product. Catalyst filtration time should be minimized toensure maximum product throughput and production rates. Cycle timeadvantages gained from a high activity catalyst can be lost if catalyst

filtration becomes an extended and time consuming step.

A catalyst should exhibit high attrition resistance to reduce catalyst lossesresulting from generation and loss of catalyst fines. The generation offines will also decrease the rate of filtration. There is often a trade-offbetween catalyst performance and the rate of catalyst separation. Catalystfiltration rate and attrition resistance are largely functions of particle size,particle shape, pore volume, pore size distribution, surface area and raw

material source.

6 PROCESS ECONOMICS

It is important to consider the economic viability of a catalyst and catalyticprocess early in the selection process. The economics of using asupported precious metal catalyst depend critically on catalyst turnover

number, i.e. the amount of product produced per amount of catalyst used,and on catalytic activity or turnovers per unit time. For supported catalysts


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Typical catalyst costs include catalyst fabrication, spent catalyst refining or

disposal and precious metal charges. In the case of a catalyst returned forrefining and reclamation of the precious metal, the total metal chargesshould include only metal irrecoverably lost during the catalytic process,the refining process, and due to handling. If the maximum allowablecatalyst cost per unit weight of product is known, one can back calculateto determine required reaction selectivity and/or the number of catalystrecycles necessary to make a process economically feasible.

Most of the commonly used catalyst supports, particularly carbon andalumina, are available in a wide range of particle sizes and surface areas.

6.1 Activated Carbon

Activated carbon powder is used principally as a support forcatalysts in liquid phase reactions. As carbon is derived fromnaturally occurring materials, there are many variations, each type

having its own particular physical and chemical properties.The surface areas of different carbons can range from 500 m2g-1toover 1500 m

2g

-1.

Trace impurities that may be present in certain reaction systemscan occasionally poison catalysts. The high absorptive power ofcarbons used as catalyst supports can enable such impurities to beremoved, leading to longer catalyst life and purer products.

6.2 Alumina


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6.3 Calcium Carbonate

Calcium carbonate is particularly suitable as a support forpalladium, especially when a selectively poisoned catalyst isrequired. The surface area of calcium carbonate is low but it findsapplication where a support of low absorption or of a basic nature isrequired, for example to prevent the hydrogenolysis of carbonoxygen bonds.

6.4 Barium Sulfate

Barium sulfate is another low surface area catalyst support. Thissupport is a dense material and requires powerful agitation of thereaction system to assure uniform dispersal of the catalyst.

6.5 Other Powdered Supports

Silica is sometimes used when a support of low absorptive capacitywith a neutral, rather than basic or amphoteric character isrequired. Silica-alumina can be used when an acidic support isneeded.


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VULCAN Catalytic Reaction GuideChemistry Reactions

1. Hydrogenation 1-55

1.1 C-C Multiple Bonds 1-7

1.2 Aromatic Ring Compounds 8-14

1.3 Carbonyl Compounds 15-25

1.4 Nitro and Nitroso Compounds 28-35

1.5 Halonitroaromatics 36

1.6 Reductive Alkylation's 37 & 38

1.7 Imines 39-41

1.8 Nitriles 42-47

1.9 Oximes 48-49

1.10 Hydrogenolysis 50-541.11 Other 55

2. Dehydrogenation 56-60

3. Hydroformylation 61& 62

4. Carbonylation 63-68

5. Decarbonylation 69

6. Hydrosilylation 70 & 71


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Reactant Product Metal Support Reaction

Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Pd > Pt > Rh

Rh = Ru = Ir

C > Al2O3 =

BaSO4 BaSO4 =

CaCO3

5-100 3-10 None or low

polarity solvent

Rh, Pt or Ru used for

stereoselective application. Pd

may cause isomerization

Pd C > Al203 20-100 1-10 None or low

polarity solvent

Pd very active under mild

conditions.

Pd CaCO3 > C

C > BaSO4

5-50 1-3 Low Polarity

Solvent

Doped Catalyst (Lindlar) under

mild conditions

Pt > Rh > Pd

Pd = Ru

C > AlO3 5-100 1-10 Neutral or acidic forCl, Br Neutral or

basic for others

X = OR, OCOR, Cl, Br, NHR, No

base with halogens; no acid with

others

Pd > Ru >Pt Al2O3 > CC > CaCO3

5-100 1-3 None or a Polarsolvent

Pd most common catalyst.

Ir-40; Rh-93,

100; Ru-100

None 20-80 1-5 Various Least hindered double bond

reduced. Asymmetric

hydrogenation with chiral ligands

Pt > Pd > Rh C > Al2O3 50-150 3-10 None or low

polarity solvent

Pd may give disproportionation

1.1 C-C Multiple Bonds

VULCAN Catalytic Reaction Guide


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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Rh> Pt Pt =

Ru > Pd

C > Al2O3 50-150 3-50 No solvent Rh active under mild conditions.

Pd >> Rh Al203 > C 100-150 >

150

1-50 None or low

polarity solvent

Basic promoters enhance activity /

selectivity.

Rh > Pd >

Ru

C > Al2O3 5-150 1-50 None or low

polarity solvent

Rh preferred - no selectivity

problems.

Pt >> Ir C >> Al2O3 5-150 1-50 Acidic solvent Acetic acid or alcohol/HCl

preferred.

Rh > Ru C > Al2O3 100-150 3-50 Acetic acid Pd most common catalyst.

Rh > Ru > Pt C > Al2O3 50-150 3-10 for Rh

> 50 for Ru

Low polarity

solvent

X = OH, OR, OCOR, NH2, NHR,

Rh preferred - no hydrogenolysis.

Product Reactant

Pt = Rh C >> Al2O3 30-150 3-50 None or alcohol Acetic acid may enhance activity.

1.2 Aromatic Ring Compounds



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Product Reactant Metal Support Reaction

Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Ru > Pt C > Al2O3 5-100 1-50 Low polarity

solvent

Fe2+ or Sn2+ salts promote Pt.

Water promotes Ru .

Pt C > CaCO3 5-100 1-20 Non-polar or low

polarity solvent

Modifiers required, e.g. Base, Fe2+

or Zn2+ salts.

Pd C >> Al2O3 5-100 1-10 Neutral solvent Acid causes loss of OH

Ru > Rh > Pt C >> Al2O3 50-150 1-50 Polar solvent (e.g.

water)

Ru requires high pressure.

Rh -40, 92, 93,

100 Ru-42,

100

None 25-110 1-200 Various Asymmetric Hydrogenation possible

with chiral ligands. Reduction of the

ketone also possible via

hydrosilation.

Pt C >> Al2O3 5-150 1-10 Low polarity

solvent

Modifiers required, e.g. Base, Fe2+

or Zn2+ salts.

Pd C >> Al2O3 5-50 1-10 Low polarity

solvent

Acid promotes hydrogenolysis of OH

Rh >> Ru C >> Al2O3 5-100 1-50 Low polarity or

neutral solvent

Ru requires high temperaturesand

pressures.

Pd C > Al2O3 5-100 1-10 Acidic solvent Promoted by strong acids.

Rh/Mo or

Rh/Re

Al2O3 150-200 80-100 Ethers Works bes t with 2o or 3o amides.

Poor for 1o amides.

Ru C > Al2O3 200-280 200-300 None or an

alcoholic solvent

Promoted by Sn.

1.3 Carbonyl Compoun ds



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Pd = Pt > Rh C 50-100 3-50 Low polarity

solvent

Bases often inhibit reaction. Prduct

amine may poison catalyst.

Reactant Product

Pd C >> Al2O3 5-100 1-10 Low polarity

solvent

Acids normally prevent dimer

formation.

Pd = Pt C > Al2O3 5-50 1-5 Various Neutral conditions

Pt > Pd = Ir CaCO3 > BaSO4

BaSO4 > Al2O3

5-100 1-5 Various Use N- or S- compounds as

moderators

Pt C 50-150 Pt > Ru C >> Al2O3 50-100 1-10 Polar or low

polarity solvent

In presence of base.

Pd >> Pt C 5-100 1-10 Low polarity

solvent

Acetic acid/mineral acid solvent

preferred

Pd = Pt C > Al2O3 5-50 1-10 Various Neutral or mildly acidic conditions

preferred

1.4 Nitro & Nitroso



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)Pt >> Rh = Pd C 5-100 1-10 Low polarity

solvent

X = halogen F >> Cl > Br > I.

Stability to hydrogenolysis

1.5 Halonitroaromatics



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Metal Support Reaction

Temp.

Reaction

Pressure

Solvents COMMENTS

Reactant Product (deg. C) (BAR)

Pd = Pt C >> Al2O3 50-150 3-50 Low polarity

solvent

Schiff base formulation catalysed

by acid.

Pd = Pt C >> Al203 50-150 1-50 None or low

polarity solvent

Often add ketone and more

catalyst after nitro reduction

1.6 Reductive Alkylations



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Temp.

Reaction

Pressure

Solvents COMMENTS

Pt C >> Al2O3 50-150 3-50 Low polarity

solvent

Acidic conditions favored.

Product Reactant

Ir-93, Rh-93,

100, Ru-100

None 25-170 1-200 DMF, Ethanol Asymmetric hydrogenation possible

with chiral ligands.

Pt C 50-100 3-50 Various Acetic acid or ethanol best.

1.7 Imines



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Pd = Rh > Pt C > > Al2O3 50-100 1-10 Acidic solvent or

additionof excess

ammonia.

Best Solvent is alcohol plus 1-2

equivalents of HCl or H2SO4

Rh C > > Al2O3 5-100 '1-10 Neutral solvent Rh gives good selectivity.

Pd > > Pt C >> Al2O3 5-100 1-10 Neutral solvent Pd gives best selectivity.

Pd C > Al2O3 5-100 1-10 Alcohol/acid or acetic

acid

Best solvents - acetic acid or alcohol

+ HCl or H2SO4

Pt > Pd C >> Al2O3 5-100 1-10 Low polarity solvent Use Neutral low polar solvents

Pd C 5-100 1-10 Alcohol with water &

acid

Imine intermediate hydrolyzed by

water.

1.8 Nitriles



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Rh >> Pd C > > Al2O3 5-100 1-10 Various Alcohol + Acid or ammonia to

minimize coupling reactions

Pd > > Rh C >> Al2O3 5-100 1-10 Acidic solvent Mineral acid/acetic acid or mineral

acid/alcohol

1.9 Oximes



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Pd C > > Al2O3 5-100 1-10 Low polarity solvent X = Cl, Br or I. Basic conditions

favored.

Pd C >BaSO4 5-50 1-3 Nonpolar solvent Reflux. Use N- or S- compounds as

modifiers + halogen aceptors.

Ru C > Al2O3 200-280 200-300 None or an alcoholic

solvent

Promoted by Sn.

Reactant Product

Pd > PtPt = Ru > Rh

C > Al2O3Al2O3 = CaCO3

50-150 3-50 Basic solvent for Cl &Br; acidic for others

X = OR, OCOR, Cl, Br, NHR. Withhalogens use alcoholic KOH or

NaOH, with others use alcoholic HCl

or acetic acid.

Pd C >> Al2O3 50-150 1-10 Acidic or neutral

solvent

X = OR, OCOR, Cl, Br, NHR. THF

Best for C-O cleavage. Aliphatic

carbonyls best for C-N cleavage.

1.10 Hydrogenolysis



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Pd C >> Al2O3 50-100 3-50 Acidic solvent Organic base may promote

selectivity.

1.11 Other



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Pd > Pt C >200 > 1 = 1 Various high

boiling point

solvents

Remove liberated H2 by N2 purge or

H2 acceptor in liquid phase.

Pd > Pt C > Al2O3 50-300 < 1 No solvent Pd is the only active catalyst.

Pd-62, 111 None 40-80 1-5 Methanol/water E = O, NH. Perform in presence of

reoxidant, e.g.Cu(Oac)2/O2.

Pd C 180-250 > 1 = 1 High Boiling Use dinitrotoluene as H2 acceptor.

Pd C > Al2O3 180-250 < 1 High Boiling

2. Dehydrogenation



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Rh-42, 43, 50,112

None 50-150 10-50 Aldehydes ortoluene

Higher normal to iso-aldehyde ratiosobtainable with Rh than with Co.

PPh3:Rh > 50:1 = 50:1

Pd-100, 111 None 50-150 10-50 Various. Base

promoted

X = Br, I R = aryl, benzyl, vinyl

Base promoted

3. Hydroformylation



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Pd-100, 101; Pt-100;

Rh-40, 112

None 50-150 10-50 Alcohol Use SnCl2 promoter for Pt and Pd.

Pt active for terminal alkenes only.

Pd-92, 100, 111 None 50-150 1-20 Various. Base

promoted

E = O, NH X = Br, I R = aryl,

benzyl, vinyl Base promoted

Pd-100, Rh-112,

RhI3

None 100-150 1-50 Carboxylic acids

(Rh) or ketones

(pd)

Iodide promotes Rh for !o alcohols.

Acidss promote Pd for 2o alcohols.

Product Reactant

Pd-100, 101, 111 None 25-100 1-10 Various Organic base such as Et3N, Bu3Nor inorganic bases such as

K2CO3. Ligand such as PPh3 also

required if Pd-111 is used.

Pd-100, 101 None 25-100 1-10 DMF Organic base such as Et3N, Bu3N

or inorganic bases such as

Pd-100, 111 None 50-150 1-20 Alcohol R = aryl Cu or Co promoted

4. Carbonylation



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Product Reactant

Rh-100 None 50-150 ca. 1 Various Also possible to decarbonylatesome acyl alcohols.

5. Decarbonylation



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Pt-92, 96, 112,

114

H2[PtCl6]

None 25-75 Ambient None,

hydrocarbons

Rh-93, 100 None 25 Ambient MeCN Z isomer obtained with EtOH or

propan-2-ol. PPh3 also requiredas

li and when Rh-93 used.

6. Hydrosilylation



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Product Reactant

Pd-62, 92, 100, 101,

111

None -10-80 ca. 1 Various M = Li, Mg, Zn, Zr, B, Al, Sn, Si,

Ge, Hg, Ti, Cu, Ni.

Pd-92, 100, 111 None 50-150 1-3 Amine or toluene X = Br, I, Otf. Base required as HX

Scavenger.

Pd-92, 111 None 25-100 - Various Organic and inorganic bases can

be used. Various ligands can be

Pd-62, 92,101, 106,

111

None 25-100 - Various Phosphineligand required where

Pd-62, 92, 111 are used. Base

required.

7.1 Heck



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Product Reactant

Pd-92, 101, 111 None 25-100 - Various Base required, generally inorganic.

Various ligands can be used in

conjunction with Pd precursor e.g.

PPh3, P(o-to)3, t-Bu3P.

7.2 Suzuki



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Product Reactant

Pd-92,111, 106 None 80-100 - THF, toluene Base required, t-BuONa orCs2CO3. Ligand such as P(o-to)3,

t-Bu3P, BINAP required when Pd-

92 or Pd-111 used.

Pd-92, 111 None 80-100 - toluene Specialist ligand required. Base

such as K3PO4, NaOH required

when R'OH used as substrate.

7.3 Buckw ald-Hartwig



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Reactant Product

Pd-100, 101 None 25-reflux - DMF, THF Addition of CuI as a co-catalyst

activates acetylene by formation of

copper acetylide. Organic base e.g.,NR3 usually used.

Pd-111 None 25-100 - DMF Base required K2CO3 or Na2CO3,

Bu4NClalso required. Reaction

performed under phase transfer

conditions, hence the need for

Pd-100 None 65 - THF Use Cul as additive.

Pd-62, 100, 111 None 25-reflux - NHEt2, NEt3 The addition of Cul as co-catalyst

activates the acetylene by formation of

a copper acetylide. Poor results are

obtained without Cul. The use of

amines is critical.

7.5 Sonogashira



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Reactant Product

Pd-62, 111 None 40-80 1-5 Methanol/water E = O, NH, Perform in presence of

reoxidant, e.g., Cu(Oac)2/O2

Pd-92, 111 None 25-100 - Toluene, THF,

dioxane

Base required NaOtBu, K3PO4

enerall used S ecialist li and

Ru-120 + prop-2-yn-1-

ol, NaPF6 + P(Cy)3

None 25-80 Ambient Toluene,

dichloromethane

Pd-62 None 65 - THF Use LiCl as additive. Use of a mild

reoxidant such as benzoquinone is

required.

Pd-62, PdCl2 None 65 - THF Use NaCO3 or NaH as additives.

Product Reactant

PdCl2 None 80 - Acetonitrile

Pd-111, PdCl2 None 25-65 - THF Lithiation of the alcohol using n-

BuLi in THFis requried as the initial

step. Palladium precursor used inconjunction with PPh3.

Pd 92 101 111 None 25 65 THF Ligand required when using Pd 92

7.6 Other



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Product Reactant

Pd-111; Rh-110, 115 None 20-50 ca. 1 Various Asymetric cyclopropanation

possible with chiral ligands.

8. Cyclopropanation



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Product Reactant

Ru-100, 130 None 25-110 Ambient MeCN, PhCl,

toluenedichloromethane

N-methyl-morpholine-N-oxide or

oxygen used as co-oxidant.TEMPO also required as ligand

when Ru-100 used.

Pt, Pd, Ru C, Al2O3 30-70 1-3 Toluene,

hydrocarbons

Use air as oxidant.

Pt, Pd, Ru C, Al2O3 '30-70 1-3 Toluene,

hydrocarbons

Use air as oxidant.

Ru-100, 130 None 25-110 Ambient MeCN, PhCl,

toluene

dichloromethane

N-Methyl-morpholine-N-oxide

oroxygen used as co-catalyst.

TEMPO also required as ligand

when Ru-100 used.

Pt > Pd C 40-60 1-5 Aqueous Basic pH (8-10) essential.

9.1 Alcohols to Carbonyls



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Product Reactant

OsO4/K2[OsO2(OH)4]

None 0-50 ca. 1 t-butanol, water,THF

Oxidants such as N-methylmorphine N-oxide or

K3Fe(CN)6 preferred. Asymetric

hydroxylation possible with chiral

l i ands.

9.2 Dihydroxylation of Alkenes



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Product Reactant

Pd-111 None 20-50 1-5 Acetic acid oralcohol

O2 or H2O2 used as oxidant.Cu2+ co-catalyst.

9.3 Oxygen Insertion Reactions



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Temp.

Reaction

Pressure

Solvents COMMENTS

(deg. C) (BAR)

Product Reactant

RuCl3, Ru-100 None 25-70 ca. 1 Various H2O2 or NaOCl oxidant.

PdCl2 None - - Water, DMF. Aq.

HCl

Use CuCl2/O2 as additives.

9.4 Other



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g Bh Evul Can Catalytic Reaction Guide