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DISCONNECTION APPROACH
“Is reverse of the synthetic steps or reactions”

Organic chemistry is always the reaction between soft negative and soft positive charges
(HSAB Principle).

The aim of this module is to let you all know! How to use, some “name reactions” (to
scheme) to build larger molecules from smaller available/precursor ones.

You can use these methods as a hand tool to answer questions in


JAM/CSIR/GATE/SET exams.

*The regio-, chemo- ,stereo-selective and protection shortcut section to this will be
posted in next part.

The SYNTHONS are generalised fragments, usually ions, that are produced by a disconnection.

α,β –Unsaturated Ketones(TM)


i) Always cleave the α,β- unsaturated double bond first.
ii) Place two units -ve charge on arm bearing the carbonyl group and two units +ve
charge on the other arm.
iii) Add two proton to the –vely charged arm and an oxide O2- to the +vely charged
arm.
iv) Now to build the TM! Always use Ald-ol condensation reaction.

For example:

Alcohols(TM)
i. Always create a carbonyl bond by detaching the proton from –OH.
ii. Cleave the alkyl / aryl for which the corresponding Grignard reagent (RMgBr) is easier
to make from its respective alkyl/aryl halide.

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iii. Now, to build the TM from starting materials, use the Grignard reagent with the
carbonyl and follow it up with acidic workup.
iv. This can even to applied to cyanohydrins, where the starting materials become carbonyls
and CN-.

For example:

1,5 diketones(TM)
i) Always number the carbonyl carbons from 1-5.
ii) Cleave the C3-C4 bond, put +ve on one arm and –ve at another arm(as shown
below).
iii) The –vely charged synthon is the enolate (now think how to make enolates!)
iv) The +vely charged arm becomes a α,β –unsaturated ketone.
v) To build the 1,5 diketone (TM) use Michael condensation reaction.

Caution! The carbonyl carbons can also be from esters, acids and enolate type
carbaanions from nitro substituted alkyls etc.

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1,3 diketones(TM)
1) Always number the carbonyl carbons from 1-3.
2) Cleave the C2-C3 bond, put +ve on one arm and –ve at another arm (as shown
below).
3) The –vely charged synthon is the enolate (now think how to make enolates!)
4) The +vely charged synthon becomes a ester/ acid chloride.
5) To build the 1,3 diketone (TM) use Claisen (External/Internal) condensation
reaction.

Caution! The carbonyl carbons can also be from esters, acids and the enolate type
carba-anions from nitro substituted alkyls etc.

Acids
i) Always try to cleave the hydroxyl bond (-OH) and generate a CO2 molecule.
ii) The alkyl left after CO2 cleavage is our synthon for Grignard reagent/ Or Sodium
acetanilides in case of alkynes.
iii) Now react CO2 with Grignard reagent /Sodium acetanilides ( are generated by
reaction of acetylenes with Na) , followed by acidic workup!

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Asymmetric ketones
i) For asymmetric ketones joined to primary and a tertiary or secondary alkyl group.
ii) Convert the C=O to C-OH by transferring one alkyl group from the adjacent
tertiary/secondary alkyl arm to C=O. {This is an example of functional group
intercoversion (FGI)}. FGI= the operation of writing one functional group for
another so that disconnection becomes possible
iii) Now to build the molecule (TM), think of Pinacol-Pinacolone rearrangement.

Caution! Pinacol –Pinacolone /Quasi Pinacol –Pinacolone (which involve diazonium ion)
are all driven by the generation of the most stable carbocation. The migratory effects of the
negative anions or groups do not control the product formation.

Diels –Alder reactions


i) If the diene and the dienophile are both unsymmetrical the Diels-Alder addition
may occur in two ways:

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