Ushering in a New Year

Chemistry Level 4

In hope of a less inflammatory year that mends the divide within communities across the globe we turn to the synthesis of a compound W that has a similar structure to the promising new anti-inflammatory drug Licofelone that possesses the following structure :

We start our synthesis using the methyl ester of proline . It undergoes the following set of reactions, a key step involves a Huisgen cycloaddition

  • It reacts with Acetyl Chloride to give A .
  • A reacts with a mixture of M e 3 S n O H Me_{3}SnOH and C 2 H 4 C l 2 C_{2}H_{4}Cl_{2} to give B . It is known to us that B possesses the formula C 7 H 11 O 3 N C_{7}H_{11}O_{3}N .
  • B reacts with acetic anhydride on slight heating to form a compound C .
  • C reacts with 2,2'-(1,2-Ethynediyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) to expel C O 2 CO_{2} and gives us the product D whose formula was determined to be C 20 H 33 O 4 B 2 N C_{20}H_{33}O_{4}B_{2}N
  • D reacts with 2 moles of P h I PhI in presence of Bis(triphenylphosphine)palladium(II) dichloride to give us the final compound W

We now define certain variables (all numbers are positive) :

  • a is the number of rings in C
  • b is the number of boron atoms in W
  • c is the number of rings in B
  • d is the difference between the number of signals in the C 13 {C}^{13} NMR and the H 1 {H}^{1} NMR of the compound W

What is the value of a b c d + 1 \overline{abcd} + 1 ?

Hint :

Compound C has no amide group


The answer is 2017.

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1 solution

We start our deductions from the methyl ester of proline whose structure is as follows :

The formation of A is a simple acetylation reaction, by observing that A has a formula C 8 H 13 O 3 N C_{8}H_{13}O_{3}N , one can deduce that the reaction conditions favour a selective removal of the methyl group to generate a carboxylic acid B .

The next set of deductions start from compound D whose formula is known, the reaction conditions that lead to the formation of D favour a Huisgen cycloaddition (The alkyne and expulsion of C O 2 CO_{2} give this away), hence we find the formula of compound C to be C 7 H 9 O 2 N C_{7}H_{9}O_{2}N . This tells us that the transformation of compound B to C is a simple dehydration reaction that should result in a ketene . However, the hint provided tells us that no amide group is present in C implying that the ketene reacts to form a mesoionic bicyclic compound.

With most of the compound present, deducing the structure of W is a simple task. Knowing that W has a similar backbone as Licofelone , the large boron rings must be replaced with phenyl rings.

From the illustrations,

  • C has 2 rings
  • W has 0 boron atoms
  • B has 1 ring
  • W has 16 C 13 {C}^{13} signals and 10 H 1 {H}^{1} signals

The answer is 2016 + 1 = 2017 \boxed{ 2017 }

Inspirations :

Professor D.M. Volochnyuk's problem in the 49 t h {49}^{th} IMO.

Awesome problem ! Keep posting :)

Sumanth R Hegde - 4 years, 4 months ago

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