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Aldehydes Ketones and Carboxylic Acids question

2022 · 29 Jul · Shift 2 · Q22
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Aldehydes Ketones and Carboxylic Acids question

2022 · 29 Jul · Shift 2 · Q22

JEE MainChemistryAldehydes Ketones and Carboxylic AcidsNumerical+4 / −1
The number of stereoisomers formed in a reaction of (±)Ph(C=O)C(OH)(CN)Ph(±)\mathrm{Ph}(\mathrm{C}=\mathrm{O}) \mathrm{C}(\mathrm{OH})(\mathrm{CN}) \mathrm{Ph}(±)Ph(C=O)C(OH)(CN)Ph with HCN\mathrm{HCN}HCN is ‾\underline{\hspace{2cm}}​. [\left[\right.[ where Ph\mathrm{Ph}Ph is −C6H5-\mathrm{C}_{6} \mathrm{H}_{5}−C6​H5​]
Numerical answer
View written solutionFree

Correct answer: 3

  1. Understand the substrate

The given compound is

(±) PhCOC(OH)(CN)Ph(\pm)\,\mathrm{PhCOC(OH)(CN)Ph}(±)PhCOC(OH)(CN)Ph

This is a cyanohydrin-containing ketone. The structure can be viewed as:

Ph−CO−C(OH)(CN)−Ph\mathrm{Ph-CO-C(OH)(CN)-Ph}Ph−CO−C(OH)(CN)−Ph
  • The carbonyl carbon of the ketone is planar and can react with HCN\mathrm{HCN}HCN.
  • The adjacent carbon C(OH)(CN)Ph\mathrm{C(OH)(CN)Ph}C(OH)(CN)Ph is already a stereogenic center because it is attached to:
    • OH\mathrm{OH}OH
    • CN\mathrm{CN}CN
    • Ph\mathrm{Ph}Ph
    • COPh\mathrm{COPh}COPh

Since the compound is given as (±)(\pm)(±), the reactant is a racemic mixture of two enantiomers.


  1. What happens on addition of HCN?

HCN adds to the ketone carbonyl:

Ph−CO−C∗(OH)(CN)Ph→HCNPh−C(OH)(CN)−C∗(OH)(CN)Ph\mathrm{Ph-CO-C^*(OH)(CN)Ph} \xrightarrow{HCN} \mathrm{Ph-C(OH)(CN)-C^*(OH)(CN)Ph}Ph−CO−C∗(OH)(CN)PhHCN​Ph−C(OH)(CN)−C∗(OH)(CN)Ph

Now the former carbonyl carbon also becomes a stereogenic center because it gets:

  • OH\mathrm{OH}OH
  • CN\mathrm{CN}CN
  • Ph\mathrm{Ph}Ph
  • the adjacent substituted carbon

So in the product there are two stereocenters.


  1. Maximum possible stereoisomers

With 2 stereocenters, the maximum number is:

22=42^2=422=4

These would normally be:

  • (R,R)(R,R)(R,R)
  • (S,S)(S,S)(S,S)
  • (R,S)(R,S)(R,S)
  • (S,R)(S,R)(S,R)

  1. Check for meso possibility

The product has the general form:

Ph−C(OH)(CN)−C(OH)(CN)−Ph\mathrm{Ph-C(OH)(CN)-C(OH)(CN)-Ph}Ph−C(OH)(CN)−C(OH)(CN)−Ph

Both stereocenters have the same set of substituents. Therefore, the (R,S)(R,S)(R,S) and (S,R)(S,R)(S,R) forms are actually the same meso form due to an internal plane of symmetry.

Hence, total distinct stereoisomers are:

  • one meso form
  • one pair of enantiomers

So total number of stereoisomers:

333
  1. Effect of starting with a racemate

Since the starting material is (±)(\pm)(±), both enantiomers are present and reaction at the planar carbonyl carbon gives all possible product stereoisomers. Distinct products remain the same count: 3.


  1. Final answer
3\boxed{3}3​

The derived answer matches the stored correct answer.

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