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    CHEM F311 Lecture 2 Oxiding and Reducing Agents 7 Aug 2024

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    CHEM F311 Lecture 2 Oxiding and Reducing Agents 7 Aug 2024

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    CHEM F311 Lecture 2 Oxiding and Reducing Agents 7 Aug 2024

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    f20221102

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    of 16

    CHEM F311 Organic Chemistry – III

    Lecture 2 – 07th Aug. 2024


    Recap

     Introduction to organic synthesis

     Greatest organic chemists

     Drug Discovery pipeline

     Rationale behind organic synthesis

    Preview
     Some common oxidizing and reducing agents

     Sodium borohydride / Lithium aluminum hydride

     Ozone, m-CPBA, NBS, NaIO4


    What is reagent???
    A substance or mixture for use in chemical analysis or other reactions
    (Source: http://www.oxforddictionaries.com)

    Oxidation States/oxidation levels


    Oxidation: loss of electrons; reduction: gain of electrons.

    Easy for inorganic salts


    – CrO42- reduced to Cr2O3
    – MnO2 oxidised to KMnO4

    But for organic compounds


     Oxidation: loss of H2, gain of O, O2, or X2

    -
    AcOH
    Some common oxidizing agents
    Oxidizing agents Acts on:
    Chromic acid Na2Cr2O7 / H2SO4 alcohol
    CrO 3, pyridine, HCl

    Permanganate conc. KMnO4,¯OH, heat C=C, CC


    dilute KMnO4, MnO2
    Osmium tetraoxide OsO4 C=C

    Ozone O3 C=C, CC

    Peroxy acids m-CPBA C=C


    (meta-chloroperoxybenzoic acid)

    Peroxide H2O2 various compounds

    N-bromosuccinimide NBS C=C


    Some common reducing agents

    Reducing agents Acts on:

    Catalytic H2 / Pt, Pd or Ni C=C, CC,C=O


    Hydrogenation

    Hydroboration BH3 / THF C=C, CC

    Dissolving Metal Na / NH3 (liq.) CC


    Li / NH3 (liq.)

    Metal Hydride NaBH4 / alcohol C=O


    LiAlH4 / ether C=O
    DIBAL / hexane C=O

    Others Zn / HOAc Molozonide


    (CH3)2S
    Some well known reagents
    NaBH4

    LiAlH4

    O3 Reactions????????

    m-CPBA

    NBS

    NaIO4
    NaBH4 and LiAlH4 (LAH): Reducing reagents

    The key difference is


    that LiAlH4 can reduce esters,
    amides and carboxylic
    acids whereas NaBH4 cannot
    reduce them.
    Mechanism for conversion of ketones to alcohols using NaBH4 and LiAlH4

    LiAlH4 is a stronger reducing agent than NaBH4 because the Al-H bond in the LiAlH4 is
    weaker than the B-H bond in NaBH4. This makes the Al-H bond less stable. The reason
    for this is low electronegativity of Aluminum (χ = 1.61) compared to Boron (χ = 2.01).
    Ozone (O3): Oxidation through C=C bond cleavage

    Reductive ozonolysis using 3


    eqt.s of pyridine as additive

    Org. Lett. 2012, 14, 9, 2242–2245


    Mechanism…..

    Ozone can be used to


    synthesize 3° alcohols, from
    alkanes, in the presence of silica
    gel, which adsorbs ozone well
    at low temperatures. Under
    similar conditions, amino group
    can be oxidized to nitro group.
    Ozone can also be used to oxidatively cleave alkynes, in which case carboxylic
    acids are formed. If the alkyne is a “terminal” alkyne (that is, has a hydrogen
    attached to one of the sp-hybridized carbons) then the product is CO2.

    In the second step during hydrolysis, if zinc is added it leads to formation of


    diketones.
    meta-Chloroperoxybenzoic acid (mCPBA): oxidizing reagent

    Prilezhaev reaction

    Stereospecific syn addition is constantly observed

    mCPBA
    Baeyer Villiger
    Oxidation

    2.5 Eqts H2O2


    Synlett. 2006, 7, 1100–1104
    Prilezhaev reaction takes place at the terminal oxygen atom of the
    peroxyacid, and the π HOMO of the olefin approaches the σ* LUMO of
    the O-O bond. (butterfly transition structure).
    BV Oxidation Mechanism…..
    N-Bromosuccinimide (NBS): Brominating & oxidizing reagent
    Electrophilic addition

    Radical substitution

    Org. Synth. 1976, 55, 27

    Selective Oxidation
    Tet. Lett. 1979, 20, 30, 2745 – 2748

    Benzenesulfonyl amine 1,8-Diazabicyclo(5.4.0)undec-7-ene


    Org. Lett. 2013, 15, 20, 5186 – 5189

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