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    Carbon-Carbon Bond Formation

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    FaTin AziEyati
    This document discusses various carbon-carbon bond forming reactions including alkylation of enolates, enamines, and heteroatom stabilized anions. It specifically covers enolate formation and reactivity, regioselectivity of enolate formation, and alkylation of enolates. It also discusses carbon-carbon bond formation using enamines, hydrazones, sulfones, and sulfoxides. Finally, it discusses carbon-carbon double bond formation reactions including aldol condensation, Wittig reaction, Peterson olefination, and the Mannich reaction.

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    Carbon-Carbon Bond Formation

    Uploaded by

    FaTin AziEyati
    117 views18 pages
    This document discusses various carbon-carbon bond forming reactions including alkylation of enolates, enamines, and heteroatom stabilized anions. It specifically covers enolate formation and reactivity, regioselectivity of enolate formation, and alkylation of enolates. It also discusses carbon-carbon bond formation using enamines, hydrazones, sulfones, and sulfoxides. Finally, it discusses carbon-carbon double bond formation reactions including aldol condensation, Wittig reaction, Peterson olefination, and the Mannich reaction.

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    Carbon-carbon Bond Formation

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    This document discusses various carbon-carbon bond forming reactions including alkylation of enolates, enamines, and heteroatom stabilized anions. It specifically covers enolate formation and reactivity, regioselectivity of enolate formation, and alkylation of enolates. It also discusses carbon-carbon bond formation using enamines, hydrazones, sulfones, and sulfoxides. Finally, it discusses carbon-carbon double bond formation reactions including aldol condensation, Wittig reaction, Peterson olefination, and the Mannich reaction.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    117 views18 pages

    Carbon-Carbon Bond Formation

    Uploaded by

    FaTin AziEyati
    This document discusses various carbon-carbon bond forming reactions including alkylation of enolates, enamines, and heteroatom stabilized anions. It specifically covers enolate formation and reactivity, regioselectivity of enolate formation, and alkylation of enolates. It also discusses carbon-carbon bond formation using enamines, hydrazones, sulfones, and sulfoxides. Finally, it discusses carbon-carbon double bond formation reactions including aldol condensation, Wittig reaction, Peterson olefination, and the Mannich reaction.

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    Carbon-carbon bond formation

    O C-C Bond Formation


    O Alkylation of enolates, enamines and

    hydrazones
    O Alkylation of heteroatom stabilized
    anions
    O C=C Bond Formation
    O Claisen rearrangement
    O Wittig reaction
    O Peterson olefination

    Alkylation of enolates
    O Enolates:
    O -deprotonation of a ketone, aldehyde or ester by

    treating with a strong non-nucleophilic base


    O The carbonyl group will stabilizes the resulting
    negative charge
    O Common bases: NaH, EtONa, NaNH2
    base

    enolate

    O Enolate formation
    O Acid catalyzed (thermodynamic)
    H+
    more substituted

    O Based induced (thermodynamic or

    kinetic)
    Base

    less substituted

    O Regioselective Enolate Formation


    O Kinetic enolate deprotonation of the

    most accessable proton


    O Typical condition: a strong hindered (nonnucleophilic base)

    LDA/THF, -78C

    Li+

    O Themodynamic enolate reversible deprotonation


    to give the most stable enolate; more highly substituted
    C=C of the enol form
    O Typical Condition: RO-M+ in ROH, protic solvent allows
    reversible enolate formation

    - K+

    tBuO-K+, tBuOH

    - K+
    thermodynamic enolate

    kinetic

    more substituted alkene

    O Alkylation of enolates:
    O Primary alkyl halides, alylic and benzylic halides work well
    O Secondary halides can be troublesome
    O Tertiary halides dont work
    O Rate of alkylation is increased in more polar solvents

    1. LDA, THF, -78C


    2. Me-I

    O C-C bond formation using enamines


    O Advantages: mono alkylation usually gives product from

    kinetic enolization

    acid
    more stable, kinetic
    enamine

    less stable, thermodynamic


    enamine

    O C-C bond formation using hydrazones


    O Hydrazones are isoelectronic with ketones
    O Hydrazone anions are more reactive than corresponding

    ketone or aldehyde enolate


    O Drawback: can be difficult to hydrolyze

    Me2N.NH 2

    LDA/THF

    H+, -H2O
    E+

    E+
    hydrolysis

    O C-C bond formation using heteroatom stabilized

    anions
    O Sulfones
    LDA/THF

    Al(Hg)

    O Sulfoxides
    LDA/THF

    Raney Ni

    C=C Bond Formation


    O Aldol condensation
    O Wittig reaction
    O Peterson olefination
    O Aldol condensation
    O Initially give b-hydroxy ketones which under

    certain conditions readily eliminated to give a,bunsaturated carbonyls

    LDA, THF, -78C

    elimination of H 2O

    O Mannich reaction formation of a,b-

    unsaturated carbonyls or a-methylene


    carbonyls

    H2C=O, Me2NH.HCl

    O Wittig Reaction
    O Reaction of phosphonium ylide with aldehydes

    and ketones
    Ph3P

    strong base

    ylide

    phosphorane

    X-

    -Ph3P=O

    betaine

    oxaphosphetane

    O Geometry of olefin
    non-stablilized ylide
    Z-olefin

    stabilized ylide
    E-olefin

    + -

    E-olefin

    O Peterson Olefination

    LDA/THF

    negative chage stabilized by Si

    -Me3SiO

    mixture of E and Z alkenes

    Show an arrow mechanism for the following reactions.

    Ph3P=CHCH2CH3
    O

    Predict the product(s) or reactant(s) for the following reactions.


    O
    1. LDA
    ?
    2. CH3CH2I

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