Stereochemistry of halogen addition to alkenes
Stereochemistry of halogen addition to alkenes
Addition of
halogen is usually predominantly trans, i.e., the addition is stereoselective (one
stereoisomer predominates over the other), e.g., the addition of bromine to maleic acid gives
–dibromosuccinic acid, which can result only from trans addition. To account
for this, Roberts et al. (1937) suggested that the first step is the
formation of a bridged (or non-classical) carbonium ion, followed by attack by
the bromide ion.
The bromide
ion attacks from behind and along the bonding C-Br+ line, and
results in a Walden inversion at this carbon atom. Since the brominium (bromonium)
ion is symmetrical, each carbon atom is attacked equally well, and consequently
results in the formation of (I) and (II) in equal amounts. (I) and (II)
are a pair of enantiomers and hence the product is a racemic modification.
The
existence of this bridged ion has been demonstrated by various workers. It
should be noted, however, that although addition is usually trans, cis
addition may also occur in certain circumstances.
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