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JEE Advanced 2021 Paper 2 · Chemistry · General Organic Chemistry and Isomerism · medium

The two geometric isomers of but-2-ene are treated separately with (i) Br2 in CCl4 (anti addition through a bromonium ion) or (ii) cold dilute…

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The two geometric isomers of but-2-ene are treated separately with (i) Br2\mathrm{Br_2} in CCl4\mathrm{CCl_4} (anti addition through a bromonium ion) or (ii) cold dilute alkaline KMnO4\mathrm{KMnO_4} or OsO4\mathrm{OsO_4} followed by work-up (syn addition). The correct statement(s) about the single compound formed, ignoring any enantiomer produced, is/are
  1. A. ciscis-But-2-ene with Br2\mathrm{Br_2} gives meso-2,3-dibromobutane
  2. B. transtrans-But-2-ene with Br2\mathrm{Br_2} gives meso-2,3-dibromobutane
  3. C. ciscis-But-2-ene with cold dilute alkaline KMnO4\mathrm{KMnO_4} gives meso-butane-2,3-diol
  4. D. transtrans-But-2-ene with OsO4\mathrm{OsO_4} followed by NaHSO3\mathrm{NaHSO_3} gives meso-butane-2,3-diol
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Answer: B, C

Anti addition to the trans alkene and syn addition to the cis alkene both place the two new groups so that the two stereocentres have opposite configurations (R,S)(R,S) with a mirror plane in the eclipsed conformation, giving the meso compound. The opposite pairings (anti to cis, syn to trans) give (R,R)/(S,S)(R,R)/(S,S), formed as a racemic mixture of chiral enantiomers. I confirmed this by building the 3D geometry of each addition and assigning CIP labels: trans plus Br2\mathrm{Br_2} gives (R,S)(R,S), cis plus KMnO4\mathrm{KMnO_4} gives (R,S)(R,S), while cis plus Br2\mathrm{Br_2} and trans plus OsO4\mathrm{OsO_4} give (S,S)(S,S). Hence A is wrong (cis alkene with Br2\mathrm{Br_2} gives the racemate), B is right (2,3-dibromobutane, meso), C is right (butane-2,3-diol, meso), and D is wrong (trans alkene with OsO4\mathrm{OsO_4} gives racemic diol). Answer: B, C.
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