Pericyclic

1. What are Sigmatropic rearrangements? Give their stereochemistry. Say

whether 5-methyl Cyclo pentadiene can offer such a rearrangement? (CSE-
1999)
2. Depict cope and Claisen rearrangements as examples of sigma tropic shift.
(CSE-1999)
3. What products would you expect to obtain from the photochemical
cyclizations of (2E, 4Z, 6E)- octatriene and of (2E, 4Z, 6Z)-octatriene? (CSE-
2000)
4. (2E, 4Z, 6Z, 8E) Decatetraene has been cyclised to 7, 8-dimethy 1-1, 3, 5-Cyclo-
octariene. Predict the manner of ring closure conrotatory or disrotatory-for
both thermal and photochemical reactions and predict the stereochemistry of
the product in each case. (CSE-2000)

5. What stereochemistry would you expect to observe in this reaction? (CSE-

2000)

a) A photochemical [1.5] sigmatropic rearrangement

b) A thermal [4.6] cyclo addition.
c) A thermal [1.7] sigmatropic rearrangement.
6. A photochemical [2, 6] cyclo addition (ii) predict the product you would expect
to obtain from the following reaction. Should this shift be a superafacial or an
antarafacial process? (CSE-2000)

7. Give stereochemistry of the product that your would expect from each of the
following electro cyclic reaction. (CSE-2001)

(i)

(ii)

Trans, trans-2, 4-hexadiene

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8. In principle one of the following Diels-Alder reactions could give endo
products, while the other give exo product explain. (CSE-2001)

a)

b)

9. Explain the following observation: (CSE-2001)

10. An adduct (A) in formed by the Diels’ alder reaction of cyclopentadiene with
ethyne. When A is treated with hexachloro cyclopentadiene (B), it forms the
well known pesticide aldrin (C). Epoxidation of C with per acid produces
another pesticide. Dieldrin (D). Draw structure of A, B, C, D and explain how
these products are formed. (CSE-2002)

11. Claisen rearrangement of allyl ether A often given product B (instead of the
expected product). How is this unwanted product formed? Addition of a
small amount of a weak base such as Ph N Me2 helps to prevent the wanted
reaction. What could be the role of the base? Explain. (CSE-2002)

12. When compound A is heated at 1500, it is transformed to compound C and

D, via a cyclic terrene (B). Propose a structure for B and describe the
process involved in the conversion of A → B, B → C and C → D. (CSE-2002)

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13. Provide mechanism for the following reactions: (CSE-2003)
(i)

(ii)

14. Give the structure of the products in the following reaction showing
mechanism: (CSE-2003)

15. (CSE-2003)

16. Suggest the possible mechanism for the conversion of 2.6-dimethyl phenyl
allyl ether (A) to 4- allyl-2, 6-dimethyl phenol (B). How will you prove that
it passes through a dienone intermediate? (CSE-2003)
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17. Rationalize the following transformation: (CSE-2004)

18. Write the mechanism of the following reaction- (CSE-2005)

(i)

19. Explain why the following 4+2 cycloaddition reaction does not occur to
produce cantharidin isolated from dried beeHes (contains resicateria). (CSE-
2005)

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20. Explain the following observation. (CSE-2005)

(i) Methyl vinyl ketones react more rapidly with cyclopentadiene than
with 1, 3-butadine in the cycloaddtion reaction.
21. Give the mechanism of the reaction that explain the following observation:

(CSE-2005)

(i) Heat in a sealed tube at 1200 C 71% D29%

Keep in contact with SnCl4 5H2O at O0 C 93% D7%
Explain your answer.
22. Illustrate different types of pericyclic reaction by taking at last one example
for each type. Explain why some of these reactions are also commonly referred
to as no reagent reactions. (CSE-2005)
23. What is a symmetry forbidden reaction? Explain the process by taking one
example of an alkene.
(CSE-2006)
24. How will you carry out the following transformation in good yields? Indicate
the reagents used conditions employed & reasons these of: (CSE-2006)

25. What are sigmatropic shifts? Give one example each of 3, 3 – and 1, 5-
sigma tropic shifts in organic reaction while explaining the logic behind such
migration. (CSE-2006)
26. Explain why on heating Cis-3, 4-dimethylcyclobutadene gives (E, Z)-
reaction-2, 4-diene while its trans-isomer gives only the (Z, E)-buta-2, 4-diene,
what happens when the same substrates are irradiated with Uv light? (CSE-
2007)
27. Explain the formation of citral through the following reaction. Sequence
via sigma tropic shift: (CSE-2006)

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28. (a) Explain the mechanism of following transformation. (CSE-2008)

b) 4 + 2 Cycloaddition is thermally allowed. Explain through HUMO and

LUMO (CSE-2008)

29. Write the structure of the product with proper stereochmical outcome, in each
of the following reactions and justify your answer with the help of FMO theory.

(CSE-2017)
30. Give the structures of E to H showing the position of the labelled carbon [*] in
each.

(CSE-2017)
31. Explain why concerted 1, 3 – sigma tropic shift of hydrogen is thermally
forbidden and give Woodward – Hoffmann selection rules for sigma tropic
rearrangement reactions. (CSE-2017)
32. Predict the products of the following reactions. (CSE-2017)

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33. How do you prepare the following compounds? (CSE-2017)

34. Identify [X] and [Y] in the following reactions. Explain their formation. 20

(CSE-2014)
35. Predict and account for the formation of stereoisomers in the following
reaction:

10 (CSE-2014)
36. Predict the product and identify the product/s in the following reaction:
(CSE-2014)

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37. Desgin a suitable experiment to establish the presence of possible
intermediate in the following reaction: (CSE-2015)

Identify the non-isolable intermediate

38. Give the Woodward –Hoffimann rule for sigmatropic rearrangement for 1,5-
shift involving hydrogen in pentadiene. Illustrate with FMO approach.
10(CSE-2014)
39. Write the product for the electrocyclic reaction of the following: (CSE-
2015)
(i) CH2 = CH – CH=CH–CH=CH2
(ii) CH3−CH3− CH=C=CH2
(iii) 2CH2=CH2

40. What will be the stereochmical course of thermal cyclization of (i)

Pentadienyl anion, and (ii) Pentadienyl cation? 10 (CSE-2017)

41. Which of the following known sigmatropic rearrangements would proceed readily
and which slowly? Explain your answer: (CSE-2018)

42. Explain the conditions for the following reaction, very briefly describe the
steps involved and comment if the reaction is reversible: (CSE-2018)

10
43. Maleic anhydride reacts rapidly with 1,3-butadiene, but does not react at all
with ethane under thermal conditions. Explain 15
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 44. Which of the following conjugated dienes would not react with a dienophlie
in Diels-Alder reaction? Justify your answer: (CSE-2018)

45. Carry out the following transformations: (CSE-2015)

46. Maleic anhydride reacts rapidly with 1,3-butadiene, but does not react at all
with ethane under thermal conditions. Explain . 15 (CSE-2015)

47.What is the name of the reactoin. (CSE-2009)

48. Sketch the mechanism of following reactions: 15×3 =45 (CSE-2010)

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49. Thermal cyclisation of cis, trans- 2, 4-hexadiene gives cis-3, 4-dimethyl cyclobutene
whereas trans, trans-2, 4-hexadiene gives trans-3, 4-dimethyl cyclobutene by the
conrotatory process. Explain using woodward Hoffmann rule. (CSE-2011)
50. Explain why (2+2) thermal cycloaddition of two molecules of ethylene to cyclobutene is
forbidden but photochemically allowed. Explain this result by using HOMO-LUMO concept.
20 ) Explain why (2+2) thermal cycloaddition of two
molecules of ethylene to cyclobutene is forbidden but photochemically allowed. Explain this result
by using HOMO-LUMO concept. 20

The exo-norborene (A) as shown below when heated gives (B) with complete retention of
configuration of the migrating group. Explain showing the mechanism.
10

The exo-norborene (A) as shown below when heated gives (B) with complete retention of
configuration of the migrating group. Explain showing the mechanism.
10

51. Trans 9, 10-Dihydronaphthalene. What is the mechanism of this transformatoin?

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. (CSE-2012)
52. Explain the mechanism of theoretically allowed concerted reaction between cis-1, 3-
butadiene with ethyleen using HOMO and LUMO; 12 (CSE-2012)
53. Complete the reaction. (CSE-2021)

54.Heating of 3-deuteroindene cause scrambling of the deuterium. Explain with mechanism.

(CSE-2021)

55. Predict the major product, and identify the type and stereochmical mode of the
following reaction: (CSE-2020)

56.(a) Complete the following conversion writing missing intermediate compounds A, B and
C : (CSE-2020)

(b) Match Column-1 (Cycloadition) with Column-II (Hukel-Mobius systems) using PMO
approach : (CSE-2021)
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Column-I Column-II

I : [2s + 2s] A = An, M, hv-allowed

II : [4s + 2a] B = A, H, Δ-allowed

III : [4s + 2s] C = A, M, Δ-allowed

IV : [2a + 2s] D = An, H, hv-allowed

Where An = Antiaromatic, A = Aromatic, M = Mobius, H = Hukel, Δ =

Thermally, hv = Photochemically.

57. Mention the reagent(s) and write the mechanism for the following conversion: (CSE-
2020)

58. Complete the conversion given below writing intermediate steps involved: (CSE-2020)

59. Write the product of the following reaction and comment on the stereochemistry of the
product: (CSE-2019)

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 Section-B
1. Each transformation show below is believed to involved a concerted reaction. In
each case show just what is happening.

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2. Each of the following transformations is believed to proceed by the indicated
sequence of concerted reactions. Show just what each step involves, and give
structure of compounds A – J.
(a) Electrocylic closure; electrocylic closure.

(b) [1, 5] – H shift; electrocylic opening.

(c) Electrocylic opening; electrocylic closure. Final product are not

interconvertible at 170 0C; be sure you account for both of them.

(d) Three electrocylic closured.

(e) A series of supra H shifts.

3. Account for the different in conditions required to bring about the following
transitions:

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4. Give stereochmical structures of K and L , and L and tell exactly what process is
talking place in each reaction.
80 −1000 C
cis, cis, cis − cycloocta -1,3,5 - triene ⎯⎯⎯⎯ → K (C8 H10 )
K + CH 3OOCC  CCOOCH 3 → L (C14 H16O 4 )
L ⎯⎯→
heat
cyclobutene + dimethyl phthalate
5. The deuterium scrambling between II and III has been accounted for on the basis
of intermolecular. Diels – Alder and retro – Diels – Alder reactions. Show how this
might occur.

(Hint: Look for an intermediate that is symmetrical except for the presence of
deuterium)
6. Suggested an explanation for each of the following facts.
(a) When the diazonium salt IV is treated with trans, trans – 2, 4 – hexadiene,
N2 and CO2 are evolved, and there is obtained stereochemically pure V.

(b) In contrast, decomposition of IV in either cis – or trans – 1, 2 –

dichloromethane yields a mixture of cis – and trans VI.
7. For each of the following reactions suggest an intermediate that would
accounted for the product. Show exact stereochemistry.

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8. (a) The diastereomeric 6, 9 dimethylspiro[4,4]Nona – 1,3 – dienes were
synthesized by reaction of cyclopentadiene with diastereomeric 2, 5 –
dibromohexanes in the presence of sodium amide. Which 2, 5 – dibromohexane
would you expect to yield each spirane?
(b) The stereochemically of the spiranes obtained was shown by comparison
of their NMR spectra, specifically, of the peaks due to the olefinic hydrogens.
Explain.
9. (a) Berson synthesized the stereospecifically labeled compound V by the
following sequence. Give structures for compounds M – R.

M + N ⎯⎯⎯⎯
Oxidation
→ O + P(both C7 H 7 DO), separated
O + LiA (OBu - t )3H, then (CH 3CO) 2O → Q + R (both C8 H11O 2 ),separated
Q is compound V on p. (1023)
(c) Berson’s study of the rearrangement of V to VI was complicated by the
tendency of VI, once formed, to decomposed into cyclopentadiene and vinyl
acetate. What kind of reaction is this decomposition?

10. (a) The sex attractant of the male bll wavelength been synthesized by the
following sequence. Give stereochmical structures for compounds S – Y.
ethylene + 3 - methyl - 2 - cyclohexenone ⎯⎯
hv
→ S (C9 H14O)
S ⎯⎯⎯⎯
bromination
→ T (C9 H13OBr)
T + C32− → U (C9 H12O)
U + CH3Li → V (C10 H12O) a single stereoisomer (Hint: Examine structure of (U)
V + 10-4 /OsO4 → W (C9 H14O), a carboxylic acid
W + excess Ph 3P = CH 2 → X (C10 H16O 2 )⎯⎯⎯⎯⎯
NaA1(OR)2 H 2
→ Y (C10 H18O), the sex attractant
(b) The stereochemistry of the sex attractant was confirmed by the following
reaction. Give a stereochmical formula for Z, and show how this confirms the
stereochemistry.
Y + Hg(OAc) 2, then NaBH 4 → Z (C10 H16 O)
11. Although “Dewar benzene”, VII, is less stable by 60 Kcal than its isomer
benzene, its conversion into benzene is surprisingly slow, with an E act of about 37
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Kcal. It has a half – life at room temperature of two days; at 90 0C complete
conversion into benzene takes half an hour.
The high Eact for conversion of VII into benzene is attributed to the fact that the
reaction is symmetry – forbidden.

12. (a) In the skin of animals exposed to sunlight 7 – dehydrochlolesterol is

converted.

What processes are actually taking place in these two reactions? Show details.
(b) An exactly analogous reaction sequence is used to converts the plant
steroid ergosterol into ergocalciferol, the vitamin “D 2that is added to milk.
ergosterol ⎯⎯
hv
→ Pre - ergocalciferol ⎯⎯⎯
warm
→ ergocalciferol

What is the structure of pre – ergocalciferol? Of ergocalciferol?

(c) On heating at 190 0C, pre – ergocalciferol is converted into IX and X
stereoisomers of ergosterol. What reaction is taking place, and what are the
structures of IX and X?
(d) Still another stereoisomers of ergosterol, XI, can be converts by ultraviolet
light into pre – ergocalciferol. What must XI be?

13. One photolysis at room temperature Trans – XII was converted into cis –XII.
When trans – XII was photolyzed at – 190 0C, browser no cis – XII could be detected
in the reaction.

Oxazoline I + n-BuLi, then CH3(CH2)5CHO → PP

PP + EtOH, H2SO4 → QQ (C11H12O3)
14. Propose a pathway for each of the following transitions:

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15. When cyclobutadiene is generated by oxidation of cyclobutadiene tricarbonyl,
most of the product is a mixture of the dimers 1and 2. Is this dimerization thermally
allowed or forbidden, and which isomer is expected to predominate?

16. Explain the following reaction:

17. Explain why cis alkenes ass 1, 3- dipoles more slowly than trans alkenes,
despite the fact that the cis ground static are higher in energy.
18. Explain the mechanistic significance of the product distribution shown:

19. What would be the stereochemistry consequence if the chiral molecule 3 were
to undergo a [1,5] – signantropic walk rearrangement, (a) if it followed the
Pericyclic allowed path, and (b) if it followed the Pericyclic forbidden path?

20. Propose a mechanism for the following rearrangement (  represents an 18O)

label):

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21. A conceivable pathway for conversion of Dewar benzene to benzene is shown
below. Classify this process as a reaction, predict whether it is thermally allowed,
and propose an experiment to distinguish it from a simple disrotatory ring opening
or a biradical cleavage of the central bond.

22. Propose a mechanism for the following transformation:

23. Specify a method of accomplishing the following transformation and propose

the mechanism.

24.Use frontier orbitals to explain why the preferred stereochemistry of the 4+6
cycloaddition of cyclopentadiene (tropone) is exo.

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