CHEM  302  

Practice  Problems  -­‐-­‐-­‐  Pericyclic  Reactions         1.    Which  Diels-­‐Alder  reaction  would  you  expect  to  proceed  at  the  highest  rate?     What  would  you  expect  the  regiochemistry  and  stereochemistry  of  the  product  to   be?     a)  
O H O H O H O H

b)    
OMe O Me

 
OMe O Me

c)  
OMe O H

 
OMe O H

    2.  In  the  first  total  synthesis  of  a  steroid,  Woodward  started  with  a  Diels-­‐Alder   reaction.  Explain  why  the  following  Diels-­‐Alder  reaction  would  form  the  first   product  and  not  the  second.      
O Me MeO O MeO O O Me not O OMe

    3.  Provide  the  mechanism  of  the  following  reaction.  Would  you  perform  the   transformation  under  thermal  or  photochemical  conditions?  Justify  your  answer.    
O

H

Me

H

 

 

 

1  

 it  is  sold  as  the  dimer  which  is  "cracked"  by  heating  at  high   temperature  (>150  °C)  to  provide  the  monomeric  species  we  use  everyday.  thermal  or  photochemical.    Upon  standing  at  room  temperature  for  extended  periods  of  time.    In  fact.    Under  what  conditions.   Cyclization  is  observed  immediately.  Suggest  which  isomer  gave  predominantly  which  product  and  explain   your  choice.  would  you  expect  the   following  reaction  to  occur?     Me Me Me Me   2 ?           2   .  cyclopentadiene  is  a  somewhat   unstable  species.  [4+2]  and  [4+4])  and  decide  what   the  most  likely  product  would  be.  provide  the   cyclization  mechanism  and  reason  for  the  stereochemistry.  The  following  alcohol  remains  stable  until  oxidation  to  the  corresponding  ketone.     Consider  possible  cycloaddition  pathways  ([2+2].  Explain  this  change  in  reactivity.       6.         7.CHEM  302     4.    Although  it  gets  used  in  synthesis  all  the  time.  when  purchased  from  a  chemical   company  like  Aldrich.     H H + hv + H H     5.   it  slowly  undergoes  a  dimerization.  The  photolysis  of  a  mixture  of  cis  and  trans  cyclododecaen-­‐7-­‐yne  gave  two   products.

    Me ! and h" H Me     10.  would  you  expect  it   to  be  stable  to  light?     H H     11.  explain  why  Dewar  benzene  does  not  easily  isomerize  to   benzene.  Dewar  benzene  (shown  below  left)  is  an  interesting  molecule.           3   .    Predict  the  product(s)  under  thermal  and  photochemical  conditions.CHEM  302     8.  Assuming  you  could  excite  an  electron  on  the  π-­‐bond.    It  is  stable  at   room  temperature.  even  though  its  isomerization  to  benzene  by  an  electrocyclic   opening  of  either  cyclobutene  ring  should  be  exothermic  by  79  kcal/mol   (approximately  the  strength  of  a  carbon-­‐carbon  bond).  Which  pericyclic  reaction  is  responsible  for  the  following  transformation?  Under   what  conditions?  Explain  the  resulting  stereochemistry.    Using  your  knowledge  of  the   Woodward  Hoffman  rules.  Under  what   conditions  (thermal  or  photochemical)  would  you  carry  it  out?         9.  State  whether  the  following  reaction  is  conrotatory  or  disrotatory.

 Explain  the  selectivity  observed  when  the  nine-­‐membered  ring  was  subjected  to   either  thermal  or  photochemical  conditions.     b)       14.             15.   CH3 R H 3C H CH3 R h! H 3C H CH3 R H 3C H CH3 R h! H 3C         4   .CHEM  302     12.  Predict  the  stereochemistry  of  the  product  under  the  given  conditions.  Predict  the  product(s)  of  the  following  reaction.     hv a)   H H       13.    Explain  the  difference  in  reactivity  in  the  following  systems.

   Predict  the  product.     O !     20.  including  stereochemistry.  Draw  a  reasonable  2-­‐step  mechanism  for  the  following  (reaction  under  thermal   conditions).    Predict  the  product.   Provide  a  mechanism. 150 °C       19.     OH c)   18.     Me O H ! MeO H MeO H H Me O       5   .     a)     b)   H H !   OH     17.CHEM  302   16.  Provide  a  mechanism  for  the  following  reactions  and  identify  the  pericyclic   process(es).  Identify  the  pericyclic  process(es)  involved  in  the  following  transformation.     OH O O O Ph CH3C(OCH3)3 H+.

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