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    Wittig Reaction

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    ruchika barwal
    The document discusses the stereo selective Wittig reaction and its applications. It introduces the Wittig reaction which generates alkenes from aldehydes and ketones using phosphonium ylides. The reaction involves preparing a Wittig reagent (ylide) and its reaction with a carbonyl compound via a phosphorus ylide intermediate. Factors like the nature of the ylide, solvent, temperature, metal ions and steric effects determine the stereochemistry of the product. Various examples are given to illustrate the reaction and its use in synthesizing biologically active molecules and natural products.

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    Wittig Reaction

    Uploaded by

    ruchika barwal
    109 views33 pages
    The document discusses the stereo selective Wittig reaction and its applications. It introduces the Wittig reaction which generates alkenes from aldehydes and ketones using phosphonium ylides. The reaction involves preparing a Wittig reagent (ylide) and its reaction with a carbonyl compound via a phosphorus ylide intermediate. Factors like the nature of the ylide, solvent, temperature, metal ions and steric effects determine the stereochemistry of the product. Various examples are given to illustrate the reaction and its use in synthesizing biologically active molecules and natural products.

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    The document discusses the stereo selective Wittig reaction and its applications. It introduces the Wittig reaction which generates alkenes from aldehydes and ketones using phosphonium ylides. The reaction involves preparing a Wittig reagent (ylide) and its reaction with a carbonyl compound via a phosphorus ylide intermediate. Factors like the nature of the ylide, solvent, temperature, metal ions and steric effects determine the stereochemistry of the product. Various examples are given to illustrate the reaction and its use in synthesizing biologically active molecules and natural products.

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    109 views33 pages

    Wittig Reaction

    Uploaded by

    ruchika barwal
    The document discusses the stereo selective Wittig reaction and its applications. It introduces the Wittig reaction which generates alkenes from aldehydes and ketones using phosphonium ylides. The reaction involves preparing a Wittig reagent (ylide) and its reaction with a carbonyl compound via a phosphorus ylide intermediate. Factors like the nature of the ylide, solvent, temperature, metal ions and steric effects determine the stereochemistry of the product. Various examples are given to illustrate the reaction and its use in synthesizing biologically active molecules and natural products.

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    You are on page 1of 33

    STEREO SELECTIVE WITTIG REACTION & ITS

    APPLICATIONS

    SUPERVISION OF PRESENTED BY
    Dr. NASEEM AHMED Naveen Kumar. K
    CONTENTS OF TALK

     INTRODUCTION

     REACTION

     MECHANISM

     EXAMPLES

     APPLICATIONS

     CONCLUSION
    INTRODUCTION

     This Wittig reaction was introduced by Georg Wittig

    He was a German chemist

     He shared the noble prize in chemistry with Herbert C. Brown in 1979

     Wittig introduced a new method for synthesis of alkenes from Aldehydes


    and ketones using phosponium ylides

     The Wittig Reaction is a very important tool in synthetic organic chemistry


    since it generates a carbon - carbon double bond normally with high level of
    Regeoselectivity
    First reaction:
    PREPARATION OF WITTIG REAGENT(YLIDE):

     The Wittig reagent is an organophosphorus reagent

    Wittig reagents are synthesized by a two-step procedure.


    GENERAL REACTION:

    O H R2
    Ph3P
    H R2 R1
    H R1
    MECHANISM:
    The factors effecting on the stereochemistry oh the olefin :

     Nature of the ylide

     Solvent effect

     Temperature

     Metal ion

    Steric effect

     Reaction conditions
    Nature of the ylide:
    REACTION:
    Wittig reaction with alpha-Alkoxy Aldehydes & stabilized ylide

    1 Bzl Bzl 75% 65:35


    2 Ac Ac 70% 60:40
    3 Ac Bzl 80% 70:30

    Above reaction in good yields but poor selectivity with 1:3 or 1:2 Z/E mixture formed

    Chem. Rev. 1989, 89, 863-927


    Improved E-Selectivity in Wittig reaction with catalyst :

    Org. Lett., Vol. 3, 2001, 3591-93


    Alkoxy Aldehydes with Ylides:
    A New Class of Phosphorus Ylides Leading to High E
    Selectivity with Semi-stabilizing Groups in Wittig Olefinations

    The yields of olefination with phenyl diazomethane were low(30%) ,partially


    due to diazo dimerisation and azine formation
     Then they are decided to generate the phenyl diazomethane in situ from the
    from the corresponding tosylhydrazone salt

    J. AM. CHEM. SOC. 2003, 125, 6034-6035


    Proposed mechanism:
    When using (MeO)3P with diazo acetate (EDA) the E selectivity was
    very much reduced (69:31, E:Z).
     then for increasing the E-selectivity they used LiBr under optimized
    condition for moving the reaction like aurbuzovtype process

    Olefination Using EDA with a Range of Aldehydes:


    They conducted a competition experiment between the stabilized ylides this
    experiment only gave olefin 1,

    2
    1:2

    Here indicating that the more hindered Ylide is substantially more


    reactive than the alkoxy -substituted ylide
    Solvent effect:
    The effect of Solvent on the Wittig reaction stereo chemistry

    SYNTHETIC COMMUNICATIONS
    Vol..33, 2187–2196, 2003
    Temperature effect
    Metal ion effect:
    LiBr
    LiBr
    Steric effect :

    J. Org. Chem. 2001, 66, 3521 3524


    APPLICATIONS:
    By using Wittig reaction biologically active molecules are prepared such as
    Chromones, N- Malayamycin A, (-)-Cleistenolide
    A Novel synthesis of 4H-chromen-4ones via intramolecular Wittig reaction:
    Preparation of Vit -A

    Total synthesis of (-)-Cleistenolide


    Total Synthesis of N- Malayamycin A :
    The geometrical Z-alkene product
    is preferred for a nonstabilized ylide, while the E-alkene is
    generally the main product when a stabilized ylide is employed.
    Traditional olefination reaction conditions that provide an excess
    of the E-alkenes include the use of a stabilized ylide and an
    aldehyde often in solvents ranging from benzene or toluene to
    DMF or DMSO. It has been recognized that Wittig reactions
    employing stabilized ylides with aldehydes proceed more slowly,
    especially in nonpolar solvents.
    LiBr
    LiBr
    transitionstate
    geometry might agree to use trigonal-
    bipyramidal phosphorus
    geometry, as specified in the two other
    mechanistic rationales
    which had been developed in detail.lg*zO
    This would require
    relatively advanced transition states with
    extensive rehybridization
    at phosphorus and carbon. However,
    recent findings do not
    support an advanced transition state, and
    reevaluation of these
    proposals is necessary.
    Tempratre effect

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