VUOS COMPANY PROFILE PARTNER FOR COOPERATION Cross coupling reactions.

VUOS

COMPANY PROFILE

PARTNER FOR COOPERATION

Cross coupling reactions

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22 VUOS – PARTNER FOR COOPERATION

AGROFERTHOLDING, a.s.

SYNTHESIA, a.s.

VUOS, a.s.

100% 100%

Cross coupling reactions

A coupling reaction in organic chemistry is a catch-all term for a variety of reactions where two hydrocarbon fragments are coupled with the aid of a metal catalyst with formation of a new carbon-carbon bond in the product.

Cross couplings involve reactions between two different partners and homocouplings couple two identical partners,

VUOS developed all types of cross couplings reactions which are widely used in the production of organic specialties mainly for production of pharmaceutical intermediates and many others organic specialties.

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AGROFERTHOLDING, a.s.

SYNTHESIA, a.s.

VUOS, a.s.

100% 100%

X

R

R'R

catalystR'BHO

HO

Example

SUZUKI REACTION

The reaction is a coupling of an aryl- or vinyl-boronic acid with an aryl-halide catalyzed by a palladium complex.

It is widely used to synthesize poly-olefins, styrenes, and substituted biphenyls.

Br BOH

OH

I

COOH

CH3

BOH

OH

COOH

CH3

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NEGISHI REACTION

The cross coupling reaction involving an organozinc compound, an organic halide and a nickel or palladium catalyst creating a new carbon-carbon covalent bond.

It can be used for syntheses of wide range of organic.

Example

R X R' Zn Xcatalyst

R'R

ZnBr

Br

CN

F3C

CN

CF3

NH2

Br

NH2

ZnCl

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KUMADA REACTION

The cross coupling is useful for generating carbon-carbon bonds by the reaction of a Grignard reagent and an organic halide.

The reaction allows many synthetic applications, especially creaction of polythiophenes, useful in organic electronic devices.

Example

R' Mg XR Xcatalyst

R R'

MgBrCH3 Cl

OC2H5

H5C2O

CH3

H5C2O

OC2H5

S

Br

BrMg

S

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HIYAMA REACTION

The reaction is a palladium-catalyzed cross-coupling reaction of organosilanes with organic halides to form carbon-carbon bonds.

This reaction has been applied to the synthesis of natural products.

Example

OSiOHO

I

R' SiR''3R Xcatalyst

R R'

CH3O

Br

CH3O

Si OH

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STILLE REACTION

The reaction is a cross-coupling an organotin compound with an sp2-hybridized organic halide catalyzed by palladium.

The reaction continues to be exploited industrially, especially for pharmaceuticals.

Example

R R'catalyst

R X R' Sn(R'')3

ClO

H3C

Sn(C4H9)3O O

H3C O

Br

CH3CH3OOC CH3CH3OOCSn(C4H9)3

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HECK REACTION

The reaction is a coupling of an unsaturated halide (or triflate) with an alkene and a base and palladium catalyst to forma substituted alkene.

This reaction is of great importance, as it allows one to do substitution reactions on planar centers.

Example

catalystR X R' R

R'

I

I

O

OH

O

OH

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SONOGASHIRA REACTION

The reaction is a cross-coupling reaction using a palladium catalyst to form a carbon–carbon bond between a terminal alkyne and an aryl or vinyl halide.

The Sonogashira cross-coupling reaction has been employed in a wide variety of areas.

Example

HC C R R' Xcatalyst

C RCR'

O

OI

O

O

OH

OH

I

I

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BUCHWALD–HARTWIG AMINATION

The reaction is used for the synthesis of carbon–nitrogen bondsvia the palladium-catalyzed cross-coupling of amines with aryl halides.

The development of the reaction allowed for the facile synthesis of aryl amines, replacing to an extent harsher methods while significantly expanding the repertoire of possible C–N bond formation.

Example

catalyst RN

R'

R''

R

X NHR'

R''

ClBr CH3NHC2H5 NBr

O

(C2H5)2NBr

H2N NH

O

(C2H5)2N

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FUKUYAMA REACTION

The reaction is a coupling taking place between a thioester and an organozinc halide in the presence of a palladium catalyst.

Advantages are high chemoselectivity, mild reaction conditions and the use of less-toxic reagents.

Example

catalystR' Zn X

R S

O

R'' R R'

O

S S

CF3

O

ZnI

O

CF3

O

S

O O

ZnCl

O

O O

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α-ARYLATION REACTION

This coupling reaction between arylhalide and organic compound containing C-O group by using a palladium-complex catalyst.

Advantages are mild reaction conditions and high chemoselectivity.

Example

Ar X

O

RR'

catalyst

O

RR'

Ar

Br

CH3

O

CH3

CH3

CH3

O

O

O

H3C

Br CH3O

O

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INTRODUCTION OF CARBOXYLIC GROUP

This reaction is a coupling between arylhalide and cabron dioxide.As catalyst can be used a palladium-complex catalyst activated with organometallic compound.

This reaction allows to expand a posibilities of carboxylic group introducing.

Example

R X CO2catalyst

R COOH

F3C CF3

Br

F3C CF3

COOH

CO2

Br

O

CO2

COOH

O

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VUOS COMPANY PROFILE PARTNER FOR COOPERATION Cross coupling reactions.

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