STEREOCHEMISTRY
ELECTROPHILIC ADDITION
Donata Pluskota-Karwatka
donatap@[Link]
Department of Chemistry of Natural Products
BASIC TERMS
Configuration arrangement of atoms in the space
Stereoisomers differ in configuration
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CHIRALITY
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CHIRALITY
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STEREOGENIC CENTRE
Stereogenic centre (centre of chirality)
*
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STEREOGENIC CENTRE
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STEREOGENIC CENTRE
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STEREOISOMERS
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STEREOISOMERS
Stereoisomers of 2,3-dibromobutane
Plane of symmetry
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CONFIGURATION R/S
-OH (1), -CH2CH3 (2), -CH3 (3), -H (4)
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CONFIGURATION R/S
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CONFIGURATION R/S
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CONFIGURATION R/S
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FISCHER PROJECTION
FISCHER PROJECTION
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come out towards us
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ALKENES
Ethylene
Propene
ELECTROPHILIC ADDITION
In electrophilic addition the π bond of the alkene and the σ bond of the
reagent are broken, and two new σ bonds are formed.
Stereochemistry
X and Y moieties can be added from the same side of the plane (syn addition)
or from the opposite sides (anti addition).
ELECTROPHILIC ADDITION
General Step 1: Attack of the π bond on the electrophile
mechanism
Step 2: Attack of the nucleophile on the carbocation
ELECTROPHILIC ADDITION
Example
ELECTROPHILIC ADDITION
ELECTROPHILIC ADDITION
Carbocations
ELECTROPHILIC ADDITION
Markovnikov’s rule:
in an electrophilic addition to an alkene, the electrophile adds in
such a way as to generate the most stable intermediate.
Carbocation stability decreases in the following order:
Inductive effect and hyperconjugation
ELECTROPHILIC ADDITION
Hyperconjugation
ELECTROPHILIC ADDITION
Carbocations stability
Adjacent carbon π bonds stabilize carbocation (Resonance)
ELECTROPHILIC ADDITION
Carbocations stability
Adjacent atoms with lone pairs stabilize carbocations
ELECTROPHILIC ADDITION
Carbocations stability
Adjacent atoms with lone pairs stabilize carbocations
ADDITION OF HYDROGEN HALIDES
HYDROHALOGENATION
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ADDITION OF HYDROGEN HALIDES
Addition of H-Br to cis-2-butenu
Mechanizm
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ADDITION OF HYDROGEN HALIDES
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CARBOCATION REARRANGEMENT
Less stable carbocation
rearrages to the more stable
Methyl group migrates to adjacent
positively charged carbon atom
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CARBOCATION REARRANGEMENT
Addition to unsymmetrical alkenes
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CARBOCATION REARRANGEMENT
Addition to unsymmetrical alkenes
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ADDITION OF HYDROGEN HALIDES
Generation of stereogenic centre
2-etylo-1-penten
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ADDITION OF HYDROGEN HALIDES
Generation of stereogenic centre
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ADDITION OF HYDROGEN HALIDES
Generation
of stereogenic centre
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HYRATION OF ALKENES
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HYRATION OF ALKENES
Mechanizm
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HALOGENATION OF ALKENES
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HALOGENATION OF ALKENES
Transition state
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HALOGENATION OF ALKENES
Stereochemistry
Enantiomers
Addition from both sides
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HALOGENATION OF ALKENES
Stereochemistry
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FORMATION OF HALOHYDIRIN
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FORMATION OF HALOHYDIRIN
Addition to unsymmetrical alkenes
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FORMATION OF HALOHYDIRIN
Regioselectivity of halohydrin formation
Thank you