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    Conformational, Steric, and Stereo-Electronic Effects Anomeric Effect

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    yayooo2004
    The document discusses several topics related to conformational, steric, and stereoelectronic effects: 1) It describes the anomeric effect which causes axial conformations to be more stable than equatorial ones in carbohydrates and other ring systems due to dipole-dipole interactions or orbital interactions. 2) Conformational stability affects reactivity, with more stable conformations typically being less reactive. For example, equatorial conformations are more stable and less reactive for acetylation. 3) Angle strain from distorted bond angles increases a molecule's reactivity by raising its ground state energy. Bicyclic systems exhibit particularly high reactivity due to angle strain. 4) Ring

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    Conformational, Steric, and Stereo-Electronic Effects Anomeric Effect

    Uploaded by

    yayooo2004
    141 views8 pages
    The document discusses several topics related to conformational, steric, and stereoelectronic effects: 1) It describes the anomeric effect which causes axial conformations to be more stable than equatorial ones in carbohydrates and other ring systems due to dipole-dipole interactions or orbital interactions. 2) Conformational stability affects reactivity, with more stable conformations typically being less reactive. For example, equatorial conformations are more stable and less reactive for acetylation. 3) Angle strain from distorted bond angles increases a molecule's reactivity by raising its ground state energy. Bicyclic systems exhibit particularly high reactivity due to angle strain. 4) Ring

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    The document discusses several topics related to conformational, steric, and stereoelectronic effects: 1) It describes the anomeric effect which causes axial conformations to be more stable than equatorial ones in carbohydrates and other ring systems due to dipole-dipole interactions or orbital interactions. 2) Conformational stability affects reactivity, with more stable conformations typically being less reactive. For example, equatorial conformations are more stable and less reactive for acetylation. 3) Angle strain from distorted bond angles increases a molecule's reactivity by raising its ground state energy. Bicyclic systems exhibit particularly high reactivity due to angle strain. 4) Ring

    Copyright:

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    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    141 views8 pages

    Conformational, Steric, and Stereo-Electronic Effects Anomeric Effect

    Uploaded by

    yayooo2004
    The document discusses several topics related to conformational, steric, and stereoelectronic effects: 1) It describes the anomeric effect which causes axial conformations to be more stable than equatorial ones in carbohydrates and other ring systems due to dipole-dipole interactions or orbital interactions. 2) Conformational stability affects reactivity, with more stable conformations typically being less reactive. For example, equatorial conformations are more stable and less reactive for acetylation. 3) Angle strain from distorted bond angles increases a molecule's reactivity by raising its ground state energy. Bicyclic systems exhibit particularly high reactivity due to angle strain. 4) Ring

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    Conformational, Steric, and Stereo-electronic Effects Part C

    1- Anomeric effect
     The incorporation of heteroatom results in Stereo electronic effects,
    conformation changes and affects the reactivity.
     From carbohydrate chemistry , pyranose sugar substituted with electron
    withdrawal ( e.g. halogen and alkoxy ) at carbon 1 is
    more stable in the axial than in equatorial ( Anomeric
    effect)

     Anomeric effect also occurs in simple ring system as 2-substituted


    tetrahydropyrans

     Anomeric effect is due to :


    1. Localized valence bond Terminology :
    Dipole-dipole repulsion between polar bonds at the anomeric carbon in
    the equatorial conformation which is
    reduced in the axial conformation
    (solvent also has effect on stabilizing this
    interaction).

    2. molecular orbital viewpoint :


    Interaction between the lone-pair electrons on the pyran oxygen and
    Orbital of the electronega ve C2 substituent.
    When the C‫ـــ‬X bond axial interaction is possible
    {antibonding Orbital of C‫ـــ‬X and the
    occupied p-type orbital on the oxygen (lone-pair
    electron)}.
     The magnitude of Anomeric effect depends on
    1. the nature of the substituent
    the more electronegative substituent, the great anomeric effect
    and the weaker bond of the substituent( easily removed).
    dielectric constant of the medium.
    2. Anomeric effect decreases with increasing dielectric constant of
    the medium (stabilizing effect of the medium will abolish the
    stability difference between axial and equatorial conformation
    (anomeric effect explana on 1 above ).
     Anomeric effect also present in acyclic systems and stabilize
    conformation that allow antiperiplanar alignment of C‫ـــ‬X bond with the
    lone-pair orbital of the heteroatom.(Exp. Conformation of Acetals ,
    Amine ).

     Because of the donor-acceptor nature of the interaction it is enhanced


    in the order F <O < N for the donor (D)(heteroatom ) and N > O > F for
    the acceptor (A) (EW substituent)
    2- Conformational effect on reactivity.
     Difference in the axial and equatorial environment (Stability) has significant
    differences in the reaction rate.
     Cyclohexane is rapidly change between axial and equatorial conformation
    (equilibrium) So large substituent (ter-butyl substituent) or rigid ring system(Trans
    decalin ) used as conformation lock to ease the effect of each conformer on the
    reaction rate.

     The effect of conformation on the reaction rate depends on the mechanism of the
    reaction:

    Axial more reactive for oxidation lower in acetylation than equatorial this is
    associated to the details of the mechanism( free energy of activation for the rate
    determining step):
    1. Oxidation(chromic acid oxidation):
    The rate determining step is breakdown of chromate ester
    intermediate. The reaction goes to the same product in both axial
    and equatorial conforma on (product with Sp2 hyperdization, with
    no conformational interaction of hydroxyl group { Diaxial
    interaction}).
    From energy diagram axial conformer has higher energy than
    equatorial one thus has lower activation energy.

    2. Acetylation :
    The rate determining step is nucleophilic attack of hydroxyl group on
    the carbonyl group of the acetic anhydride to form tetrahedral
    intermediate .

    Trans isomer have OH in equatorial so more stable (lower in energy).


    The intermediate contain acetylating agent in the equatorial (Trans)
    more stable (lower in
    energy). Energy difference
    is greater in case of acetyl
    group as it’s more bulky.
    So activation energy for
    Trans (equatorial) is less
    than axial (cis).
    Anomeric effect on reactivity Exp. CrO3 can oxidize pyranose acetals leads to Ϭ-ketoesters

    Ease of H abstract in axial isomer is more than equatorial conform and hence more
    reactive due to anomeric effect.
    3- Angle strain and its effect on reactivity.
     Angle strain : is increase of energy content of the molecule due to distortion
    of bond angles .
     Six memberd rings are nearly strain free.
     Angle strain increase ground state energy resulting in reaction which leads to
    ring opening proceeds more readily than those of unstrained ring system.
    Also it causes qualitative changes in bond hybridization leads to increase
    reactivity.
    Ex. Saturated hydrocarbons are inert to bromine while cyclopropane reacts
    readily.

    Ex. Bicyclo [1.1.0] butane has great angle strain, decrease stability and increase
    reactivity. The central bond is nearly pure P orbital and reactive towards
    electrophiles. Acid-catalyzed hydrolysis gives products characteristic of the
    bicyclobutonium Cation.

     Alkene exhibit large strain energy when bonds to the two sp2 –hybridized
    carbons not coplanar. Ex. E-cycloheptene:
     Trans geometry not allow coplanar of the double bonds’
    which leads to highly strained compound highly reactive to
    Diels- Alder reaction.
     With increase ring size amount of strain decrease as double bonds
    approaches coplanar geometry.
     Bicyclic rings also distort alkene coplanarity. Ex.
    Bicycle[2.2.1]hepta-1-ene:
     Bredt’s rule”absence of bridgehead double bonds” is not absolute as increase
    in ring size (>7 carbon) strain is lower and can exist. They are very reactive
    toward addition reaction.

    4- Relationship between ring size and rate of cyclization.


     Baldwin and co-workers classify ring closure with respect to three factors:
    o Ring size .
    o Hybridization of the carbon at reaction site.
    o Relationship (endocyclic or exocyclic )of reacting bond to the forming
    ring.

     Five membered ring endo-trig ring closure is difficult?


    The nucleophile cannot approach in the nodal plane of π system so it must
    attack from above or below which leads to distortion of ring geometry.

    While 5-end-dig cyclization is feasible as acetylenic system provide orbital in


    nearly planar approach.

    Ex.

    5- Torsional and stereoelectronic effects on reactivity


     Torsional strain nonoptimal arrangement of vicinal bonds.
     Torsional strain in transition state raises the activation energy of the reaction.
     Ex .reaction involve hybridization changes at a ring atom:

    In the above reaction sp2 carbon converted to sp3carbon:


     Five-membered ring: this increase Torsional strain.
     Six-membered ring: this decrease Torsional strain (6 strain free).

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