Fundamentals of Medicinal Chemistry

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diastereoisomers are formed, the usefulness of the reaction will also depend on

the ease of separation of these mixtures into their component isomers.

10.3 Designing organic syntheses


The synthetic pathway for a drug or analogue must start with readily available

materials and convert them by a series of inexpensive reactions into the target

compound. There are no obvious routes as each compound will present a

different challenge. The usual approach is to work back from the target struc-

ture in a series of steps until cheap commercially available materials are found.

This approach is formalized by a method developed by S Warren, which is

known as either thedisconnection approachorretrosynthetic analysis. In all cases

the final pathway should contain a minimum of stages, in order to keep costs to

a minimum and overall yields to a maximum.

10.3.1 An introduction to the disconnection approach

This approach starts with the target structure and then worksbackwardsby

artificially cutting the target structure into sections known assynthons. Each of

these backward steps is represented by a double shafted arrow (¼)) whilst

is drawn through the disconnected bond of the target structure. Each of the

possible synthons is converted on paper into a real compound known as a

reagent, whose structure is similar to that of the synthon. All the possible

disconnection routes must be considered. The disconnection selected for a step

in the pathway is the one that gives rise to the best reagents for a reconnection

reaction. This analysis is repeated with the reagents of each disconnection step

until readily available starting materials are obtained. The selection of the

reagents and the reactions for their reconnection may require extensive litera-

ture searches (Table 10.2).

In the disconnection approach, bonds are usually disconnected by either

homolytic or heterolytic fission (Figure 10.11(a) and (b) ). However, some

bonds may be disconnected by a reverse pericyclic mechanism (Figure 10.11(c) ).

Disconnections may involve either the carbon skeleton or functional groups.

Normally the first step is to disconnect the sections of a molecule that are held

together by functional groups such as esters, amides and acetals, as it is usually

easier to find reconnection reactions for these functional groups. Heterolytic

disconnections usually provide the most useful approach to synthesis design.

214 AN INTRODUCTION TO LEAD AND ANALOGUE SYNTHESES

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