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Common error alert: Alkenes and arenes that are substituted with electrophilic
groups are electrophilic at the -carbon (i.e., the C atom not attached to the elec- trophilic substituent), not at the ␣-carbon, because the electrons in the bond need to end up on the ␣-carbon in order to interact with the electrophilic group. This pattern parallels what is seen for alkenes substituted with electron-donating
groups, which are nucleophilic at the -carbon. Alkenes that are normally nucleophilic can act as electrophiles toward potent-enough
nucleophiles, and alkenes that are normally electrophilic can act as nucleophiles to-
ward potent-enough electrophiles. For example, alkyllithium compounds (RLi) add to
the “nucleophilic” alkene ethylene, and the “electrophilic” alkene 2-cyclohexen-1-one
adds Br 2 across its C– – C bond. These reactions provide additional support for de- scribing alkenes as the chameleons of organic chemistry. Common error alert: Do not confuse formal positive charge with elec-
trophilicity! Consider CH 2 – – O ϩ CH 3 . The electronegative element O has a formal positive charge, but it is not electron-deficient, so there is no reason to think that
it may be electrophilic. Now draw the resonance structure, H 2 C ϩ – O–CH 3 . O is neutral, the formal positive charge is on C, and C is electron-deficient.
Considering the two resonance structures, which atom is more likely to be at
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