H CH3

H3C 2 3 H
C C
HO OH
a pair of
H 2 3 CH3 OsO4
(2S,3S)-2,3-Butanediol enantiomers;
C C
ROOH a racemic
H3C H
HO OH mixture
trans-2-Butene 2 3
(achiral) C C
H CH3
H3C H

(2R,3R)-2,3-Butanediol

Syn hydroxylation of cis-2-butene gives meso-2,3-butanediol; because the meso

compound is achiral, the product is optically inactive. Syn hydroxylation of trans-
2-butene gives racemic 2,3-butanediol. Because the diol is formed as a racemic
mixture, the product of the oxidation of the trans alkene is also optically inactive.
Thus, the osmium tetroxide oxidation of an alkene is stereospecific; the stereo-
chemistry of the product depends on the stereochemistry of the starting alkene.
Notice that the stereochemistry of the product of the osmium tetroxide oxi-
dation of trans-2-butene is opposite to that formed on the addition of bromine to
trans-2-butene. Osmium tetroxide oxidation gives the glycol as a pair of enantiom-
ers forming a racemic mixture. Addition of bromine to trans-2-butene gives the
dibromoalkane as a meso compound. A similar difference is observed between the
stereochemical outcomes of these reactions with cis-2-butene. The difference in
outcomes occurs because bromination of an alkene involves anti addition, whereas
oxidation by osmium tetroxide involves syn addition.
In this section, we have seen two examples of reactions in which achiral start-
ing materials give chiral products. In each case, the chiral product is formed as a
racemic mixture (which is optically inactive) or as a meso compound (which is also

Figure 6.11 Step 1: Make a new bond between a nucleophile ( bond) and an electrophile Reaction of
Anti stereoselective addition of trans -2-butene with bromine forms bridged bromonium ions which are enantiomers
bromine to trans-2-butene gives +
Br H CH3
meso-2,3-dibromobutane. H CH3 Br2 H3C H
C C C C + C C
H3C H H CH3
H3C H Br
+
+

+
+
trans -2-Butene (bridged bromonium ion intermediates;
(achiral) a pair of enantiomers)

Step 2: Make a new bond between a nucleophile and an electrophile Attack of bromide on
either carbon of either enantiomer gives meso-2,3-dibromobutane

Attack of
+ bromide ion Br CH3
at carbon 3 H
C C
H Br
H3C
+ (2R,3S )-2,3-Dibromobutane
Br (meso) Identical
2 3
C C
H CH3 H
H3C H Br
H3C
C C
Br Br Attack of CH3
bromide ion Br H
at carbon 2
(2S,3R)-2,3-Dibromobutane

250 Chapter 6 Reactions of Alkenes

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