Selectivity in reaction

Aspects of selectivity in reaction pathways :

Chemoselectivity
Regioselectivity
Protection
Stereoselectivity.
Chemoselective
If an organic compound contains more than one different
functional groups or more than one like functional groups that
are not equivalent, and, if a reagent reacts exclusively or
predominately with one of them, the reaction is said to be
chemoselective.
For example, both ketones and carboxylic acids can be reduced
to alcohols.
1 contains a keto group and a carboxylic acid group. When 1 is
treated with a reducing agent, three reactions are possible.
 When 1 is treated with the reducing agent sodium borohydride ,
the only organic product observed is 2

Evidently, sodium borohydride reacts with only one of the two

functional groups in 1. Thus, the reaction of 1 with sodium
borohydride is chemoselective.
 Regioselective
If more than one reaction could occur between a set of reactants
under the same conditions giving products that are constitutional
isomers and if one product forms in greater amounts than the
others, the overall reaction is said to be regioselective

+ HBr

Experimentally, 2 is the major product; 3 is the minor

product. Thus, the overall reaction between 1 and HBr is
regioselective toward 2.
 If more than one reaction could occur between a set of reactants
under the same conditions giving products that are constitutional
isomers and if only one product is observed, the overall reaction is
said to be 100% regioselective or regiospecific.

+ HBr

The only observed product is 5. (Relative yields of 5 and 6 are 100% and
0%, respectively.) Thus the overall reaction between 4 and HBr is
regiospecific toward 5.
All regiospecific reactions are regioselective, but not all regioselective
reactions are regiospecific.
 Stereoselective
If more than one reaction could occur between a set of reactants
under the same conditions giving products that are stereoisomers
and if one product forms in greater amounts than the others, the
overall reaction is said to be stereoselective.

Experimentally, 2 is the major

product. Thus, the overall reaction between
1 and H2 is stereoselective toward 2.
Protection
A protecting group or protective group is introduced into a
molecule by chemical modification of a functional group to obtain
chemoselectivity in a subsequent chemical reaction. It plays an
important role in multistep organic synthesis.

Acetal protection of a ketone

during reduction of an ester, vs.
reduction to a diol when
unprotected.
In many preparations of organic
compounds, some specific parts of their
molecules cannot survive the required
reagents or chemical environments. Then,
these parts, or groups, must be protected.
For example, lithium aluminium hydride is
a highly reactive but useful reagent
capable of reducing esters to alcohols
It will always react with carbonyl groups. When a
reduction of an ester is required in the presence
of a carbonyl, the attack of the hydride on the
carbonyl has to be prevented. For example, the
carbonyl is converted into an acetal, which does
not react with hydrides. The acetal is then called
a protecting group for the carbonyl. After the
step involving the hydride is complete, the acetal
is removed (by reacting it with an aqueous acid),
giving back the original carbonyl. This step is
called deprotection.