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    CHM 624 Advance Organic Chemistry: Reductions

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    Johan Daniyal
    This document discusses various reduction reactions in organic chemistry. It begins by defining reduction as a chemical reaction that involves gaining electrons. It then covers hydrogenation reactions, including heterogeneous catalytic hydrogenation using transition metal catalysts and homogeneous catalytic hydrogenation using Wilkinson's catalyst. Boron and aluminum reagents that are commonly used for reduction are also described, such as sodium borohydride, lithium aluminum hydride, and diisobutylaluminum hydride. Specific examples of reduction of functional groups like carbonyls, carboxylic acids, esters, and nitro groups are provided. Other reduction methods mentioned include Clemmensen, Wolff-Kishner, and Luche reductions.

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    CHM 624 Advance Organic Chemistry: Reductions

    Uploaded by

    Johan Daniyal
    64 views29 pages
    This document discusses various reduction reactions in organic chemistry. It begins by defining reduction as a chemical reaction that involves gaining electrons. It then covers hydrogenation reactions, including heterogeneous catalytic hydrogenation using transition metal catalysts and homogeneous catalytic hydrogenation using Wilkinson's catalyst. Boron and aluminum reagents that are commonly used for reduction are also described, such as sodium borohydride, lithium aluminum hydride, and diisobutylaluminum hydride. Specific examples of reduction of functional groups like carbonyls, carboxylic acids, esters, and nitro groups are provided. Other reduction methods mentioned include Clemmensen, Wolff-Kishner, and Luche reductions.

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    CHAPTER 3

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    This document discusses various reduction reactions in organic chemistry. It begins by defining reduction as a chemical reaction that involves gaining electrons. It then covers hydrogenation reactions, including heterogeneous catalytic hydrogenation using transition metal catalysts and homogeneous catalytic hydrogenation using Wilkinson's catalyst. Boron and aluminum reagents that are commonly used for reduction are also described, such as sodium borohydride, lithium aluminum hydride, and diisobutylaluminum hydride. Specific examples of reduction of functional groups like carbonyls, carboxylic acids, esters, and nitro groups are provided. Other reduction methods mentioned include Clemmensen, Wolff-Kishner, and Luche reductions.

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    Download as pptx, pdf, or txt
    64 views29 pages

    CHM 624 Advance Organic Chemistry: Reductions

    Uploaded by

    Johan Daniyal
    This document discusses various reduction reactions in organic chemistry. It begins by defining reduction as a chemical reaction that involves gaining electrons. It then covers hydrogenation reactions, including heterogeneous catalytic hydrogenation using transition metal catalysts and homogeneous catalytic hydrogenation using Wilkinson's catalyst. Boron and aluminum reagents that are commonly used for reduction are also described, such as sodium borohydride, lithium aluminum hydride, and diisobutylaluminum hydride. Specific examples of reduction of functional groups like carbonyls, carboxylic acids, esters, and nitro groups are provided. Other reduction methods mentioned include Clemmensen, Wolff-Kishner, and Luche reductions.

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    of 29

    CHM 624

    ADVANCE ORGANIC CHEMISTRY


    ~REDUCTIONS~
    Nur Rahimah Said
    REDUCTIONS
    What????
    Reduction is chemical reaction that
    involves the gaining of electrons.

    Hydrogenation

    Boron Reagents

    Aluminium
    Reagents
    Hydrogenation
    Heterogeneous catalytic hydrogenation

    Homogeneous catalytic hydrogenation

    Catalytic hydrogenation
    H+ adds to double bonds via a catalyst
    Alkane was form
    Hydrogenation
    • Heterogeneous catalytic hydrogenation
    Transition metal absorb onto a solid support
    -metal: Pd, Pt, Ni, Rh.
    -Solid support: carbon, alumina, silica
    Sensitive to steric effects & choice of solvents
    -order of solvent reactivity:
    Hexane<EtOAc<EtOH<HOAc<HOAc/HCl)
    -polar functional groups like hydroxyl can directly
    deliver of hydrogen.
    Olefins and acetylene were reduce to saturated
    hydrocarbon - Cis addition of hydrogen
    Hydrogenation
    • Heterogeneous catalytic hydrogenation

    Direct hydrogenation
    Hydrogenation
    • Heterogeneous catalytic hydrogenation- Lindlar catalyst
     A Lindlar catalyst is a heterogeneous catalyst that consists of
    palladium deposited on barium sulfate and quinoline
    (Pd/BaSO4/quinoline).
     It is use for the hydrogenation of alkynes to alkenes (without
    further reduction into alkane)
     Pd/BaSO4/quinoline-partially poison to reduce activity: thus
    reducing only the most reactive functional group.
    Hydrogenation
    • Homogeneous catalytic hydrogenation
    Catalyst is soluble in the reaction medium
    Catalyst not “poisoned” by sulfur
    Very sensitive to steric effects
    • Reactivity: terminal olefins faster than internal
    and cis faster than trans
    Hydrogenation
    • Homogeneous catalytic hydrogenation- Wilkinson’s catalyst,
    (Ph3P)3RhCl
     Wilkinson’s catalyst- the common name for
    chlorotris(triphenylphosphine)rhodium(I)
     Its catalyzed the hydrogenation of alkene to produce the
    alkane product/ methylene groups.

    JOC 1992, 57, 2767

    Angew. Chem. Int. Ed. Engl. 1987, 26, 190


    Hydrogenation
    • Homogeneous catalytic hydrogenation is direct hydrogenation
     Regioselective hydrogenation- allylic and homoallylic alcohols
    are hydrogenated faster than isolated double bonds
    Boron Reagents
    • List of Boron hydrate
    Sodium borohydride, NaBH4 –reduce ketone, aldehyde
    Lithium borohydride, LiBH4 –reduce ketone, aldehyde,
    ester, epoxide,
    Zinc borohydride, Zn(BH4)2 –reduce ketone, aldehyde
    Tetraalkylammonium borohydride, R4NBH4-soluble in
    organic solvent (DCM)
    Sodium cyanoborohydride, Na(CN)BH3 –reduce ketone,
    aldehyde + iminium ion
    Sodium triacetoxyborohydride, Na(OAc)3BH –reduce
    ketone, aldehyde (less reactive)
    Boron Reagents
    • Using NaBH4
     Reduce aldehyde and ketone to alcohol
     Does not react with acid, ester, lactone, epoxide or nitrile.
     Additives can increase reactivity
    Na H
    H
    B
    H
    H
    Boron Reagents
    • Using NaBH4/CeCl3 – Luche Reduction
    Boron Reagents
    • Using Zn(BH4)2
    • Preparation: ZnCl2 (Ether) + NaBH4 Zn(BH4)2
    – Ether solution of Zn(BH4)2 is neutral- good for base sensitive
    compounds
    – Chelation control model
    Boron Reagents
    • Using Na(CN)BH3
     Less reactive than NaBH4
     Used in reductive amination reaction
    • The reaction related to Eschweiler-Clark Reaction, where a
    primary or secondary amine is methylated using formic acid
    and formaldehyde.
    • The reductive amination reactions will produce the
    secondary/ tertiary amine.
    • The reaction also known as Eschweiler-Clarke methylation
    Aluminium Reagents
    • List of Aluminium hydrates
     Lithium Aluminium Hydride, LiAlH4 - (LAH)
     Diisobutyl Aluminium Hydride, (iBu)2AlH - (DIBAL)
     Sodium Bis(2-methoxyethoxyl)aluminium hydride,
    Na(MeOCH2CH2O)2AlH2 - (REDAL)

    • Aluminium hydrates characteristics


    Very powerful reducing agents
    Used as suspension in Ether or THF (solvent)
    Reduce carbonyl, carboxylic acid, and ester to alcohol
    Reduce amide, nitrile, and aryl nitro groups to amine
    Reduce C-X (X= halide) to C-H
    Reduce acetylenic alcohol to trans-allylic alcohol
    Aluminium Reagents
    • Using LAH H
    Li H

    Al
    H
    H
    **Triple bond was
    reduced to double bond
    in trans configuration.
    trans

    cis

    H2O
    Aluminium Reagents
    • Using LAH- reduce carboxylic acid to primary alcohol

    (Carboxylic acid)

    Reaction usually occur in diethylether (Et2O) or tetrahydrofuran (THF )


    followed by H3O+
    The reaction is difficult and often requires heating in THF solvent to go to
    completion
    Carboxylic acid is less reactive than aldehyde, ketone or ester , to reduction
    by hydride
    Due to its low reactivity, carboxylic acid can ONLY reduced by LAH and NOT
    by less reactive NaBH4
    Aluminium Reagents
    • Using LAH- reduce acid chloride to aldehyde then to primary
    alcohol
    Aluminium Reagents
    • Using DIBAL
    Reduce ketone and aldehyde to alcohol
    Reduce lactone to hemi-acetal
    Reduce ester to alcohol
    Reduce ester to aldehyde (under control
    condition)

    DIBAL
    Aluminium Reagents
    • Using DIBAL
    Aluminium Reagents
    • REDAL as versatile hydride reducing agent
     Reduce aldehyde, ketone, carboxylic acid, ester,
    acyl halide and anhydride to primary alcohol.
     Reduce lactone and epoxide to diols.
     Reduce nitrogen derivative such as amide, nitrile,
    imines and most other organonitrogen
    compounds to amines.
     Reduce nitroarene to azoxyarene, azoarene or
    hydroazoarene depending on the reaction
    conditions.
    Aluminium Reagents
    • Using REDAL- chelation directed opening of allylic
    epoxides

    REDAL

    DIBAL
    Aluminium Reagents
    Some common functional group reductions using REDAL can
    be found below:

    REDAL
    Clemmensen Reduction
    Condition: Refluxing an aldehyde or ketone with amalgamated
    zinc, Zn(Hg) in concentrated HCl was converted the carbonyl
    group (ketone or aldehyde) to a methylene group
    Wolff-Kishner Reduction
    • to convert carbonyl group to methylene group
    •In the original procedure, the aldehyde/ketone and
    hydrazine are refluxed with KOH in a high-boiling
    solvent.
    • The same reaction can be brought using hydrazine
    and potassium tert-butoxide in DMSO.
    EASY REDUCTION

    (H.O. House Modern Synthetic Reactions, 2nd edition)

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