Scribd Logo
Upload

Welcome to Scribd!

  • 1 views

    Epoxide Reactions 250115 201953

    Uploaded by

    hasani78983fdgd23jh

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd

    Epoxide Reactions 250115 201953

    Uploaded by

    hasani78983fdgd23jh
    1 views5 pages

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    1 views5 pages

    Epoxide Reactions 250115 201953

    Uploaded by

    hasani78983fdgd23jh

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    You are on page 1of 5

    Predict Product Show stepwise mechanism

    (including
    stereochemistry)

    mCPBA

    O O
    H cat. H2SO4 H

    D D
    H 2O

    O
    O H
    H cat. H2SO4
    D
    D CH3OH

    O
    O H
    NaOH
    H D
    D H 2O

    O
    O H
    H NaOCH3
    D
    D CH3OH

    O
    O H
    H 1. CH3MgBr
    D
    D 2. H2O (or H3 O+)

    O O
    H 1. LiAlH4 H
    D D
    2. H2O (or H3O+)
    Br
    Br
    SN2 Mechanism: + NaSMe SN1 Mechanism: + HOMe
    cold

    Factor affecting rate (circle): carbocation stability, sterics, alkene substitution. Factor affecting rate (circle): carbocation stability, sterics, alkene substitution.

    Special requirements (circle): backside attack, antiperiplanar H/LG, look Special requirements (circle): backside attack, antiperiplanar H/LG, look
    for carbocation rearrangement for carbocation rearrangement

    Stereoselectivity: Stereoselectivity:

    Br Br

    E2 Mechanism: + NaOMe E1 Mechanism: + HOMe


    Δ Δ

    Factor affecting rate (circle): carbocation stability, sterics, alkene substitution. Factor affecting rate (circle): carbocation stability, sterics, alkene substitution.

    Special requirements (circle): backside attack, antiperiplanar H/LG, look for Special requirements (circle): backside attack, antiperiplanar H/LG, look for
    carbocation rearrangement carbocation rearrangement

    Regioselectivity (circle): Pull off antiperiplanar hydrogen leading to the most Regioselectivity (circle): Pull off antiperiplanar hydrogen leading to the most
    substituted alkene or always form the most highly substituted alkene possible. substituted alkene or always form the most highly substituted alkene possible.
    strong nucleophile/ weak strong nucleophile/ strong bulky base weak nucleophile/
    base strong base weak base
    Promote SN2 Promote SN2/E2 Promote E2 Promote SN1/E1
    CH3 CH3OH (MeOH)
    I– Br– HS– NC– Br–Br–

    HO– CH3 O– CH3CH2 O–


    H3C C O– O–
    NaN3 O NaOH NaOMe NaOEt CH3 H 2O
    –
    H 3C O– RS Conjugate acids CH3CH2OH (EtOH)
    tert-BuOK NaO(CH3)3
    have pKa ~ 16-18
    R2NH, RNH2 Recall, you make hydroxide KOt-Bu NaOt-Bu
    or alkoxide ions from the O
    The structures above
    Conjugate acids corresponding alcohol or
    are all ways of referring O S OH
    have pKa < 11 water and NaH.
    to the tert-butoxide ion.
    O (E1 only)
    ROH + NaH RONa + H2
    does NOT act as Nuc.

    Type of alkyl halide Mechanism(s) Conditions


    (or any RLG) Mechanism favored
    possible (circle)

    Methyl substrates
    SN1 E1 SN2 E2 ANY
    CH3Br

    strong nucleophile/weak base


    Primary (1o) substrates
    strong nucleophile/strong base
    CH3CH2Br
    SN1 E1 SN2 E2
    strong bulky base
    OTs
    Secondary (2o) substrates strong nucleophile/weak base
    strong base/strong nucleophile
    I
    SN1 E1 SN2 E2 strong bulky base
    OMs
    weak base/weak nucleophile
    Tertiary (3o) substrates strong nucleophile/strong base

    SN1 E1 SN2 E2 strong bulky base


    I
    OH2 *No SN2 - too sterically weak base/weak nucleophile
    hindered

    carbocations too unstable (sp


    Vinyl and aryl substrates hybridized C) so no SN1/E1.
    C-X bond strength high (Sp2C-
    Cl X) hinders Sn2/E2.

    Br SN1 E1 SN2 E2
    ALL
    NONE

    1o allylic or 1o benzylic substrates


    SN1 E1 SN2 E2 strong nucleophile
    Cl Br
    carbocation resonance
    stabilized - so SN1 possible weak base/weak nucleophile
    even though primary

    You might also like