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14  

Suggested  solutions  for  Chapter  14  
 
PROBLEM  1  
Are  these  molecules  chiral?  Draw  diagrams  to  justify  your  answer.  
OH
HO2C
HO2C

Ph
O

OH

OH

O

OH
O

O

O

 

Purpose  of  the  problem  
Reinforcement   of   the   very   important   criterion   for   chirality.   Make   sure  
you  understand  the  answer.  

Suggested  solution  
Only  one  thing  matters  –  does  the  molecule  have  a  plane  of  symmetry?  
We  need  to  redraw  some  of  them  to  see  if  they  do.  On  no  account  look  
for   chiral   centres   or   carbon   atoms   with   four   different   groups   or  
anything  else.  Just  look  for  a  plane  of  symmetry.  If  the  molecule  has  one,  
it   isn’t   chiral.   The   first   compound   has   been   drawn   with   carboxylic   acids  
represented  in  two  different  ways.  The  two  CO2H  groups  are  in  fact  the  
same  and  the  molecule  has  a  plane  of  symmetry  (shown  by  the  dashed  
lines).  It  isn’t  chiral.  

Me

OH

OH

Me

OH

=

HO2C

 

O

OH

HO2C

CO2H

HO2C

CO2H

 

  and   will   certainly   be   much   easier   to   see   if   you   make  a  model.   The   dashed   line   shows   the   plane   of   symmetry  at  right  angles  to  the  paper.   and   a   plane   at   right   angles   to   the   ring.  and  neither  is  the  plane  perpendicular  to  the  ring.   By   drawing   first   one   and   then   the   other   ring   in   the     .2   Solutions  Manual  to  accompany  Organic  Chemistry  2e   The   second   compound   is   chiral   but   if   you   got   this   wrong   don’t   be   dismayed.  No  plane  of  symmetry:  molecule  is  chiral.  which   contain  two  rings  joined  at  a  single   atom.  are  discussed  on  p.  as  Ph  is  on  one   side  and  H  on  the  other.  in  the  plane  of  the  page.  The  plane  of  symmetry  (shown  by  the  dotted  lines)  may  be  easier   to   see   after   redrawing.   The   final   acetal   (which   is   a   spiro   compound)   is   drawn   flat   but   the   central   carbon   atom   must   in   fact   be   tetrahedral   so   that   the   two   rings   are   orthogonal.   OH O O   ■  Spiro  compounds.  Making  a  model  would  help  but  there  are  only  two  plausible   candidates  planes  of  symmetry:  the  ring  itself.   = OH OH   The   fourth   compound   needs   only   the   slightest   redrawing   to   make   it   very   clear   that   it   is   not   chiral.   All   the   CH2   groups   are   identical   so   the   alcohol   can   be   attached   to   any   of   them.  653  of   the  textbook.   Ph H Ph Ph no plane of symmetry perpendicular to ring no plane CO2H H of symmetry CO2H in plane of page H CO2H   The   third   compound   is   not   chiral   because   of   its   high   symmetry.     The   molecule   redrawn   below   with  the  tetrahedral  centre  displayed  shows  that  the  plane  of  the  page   isn’t   a   plane   of   symmetry   as   the   CO2H  is  on  one  side  and  the  H  on  the   other.

  the   rotation   will   change   to   +6.   the   length   of   the   cell   used   in   the   polarimeter.  Only   if   the   slipper   had   been   made   of   single   enantiomers   of   a   transparent   substance   would   it   have   rotated   the   plane   of   polarized   light.  But  would  it  have   rotated  the  plane  of  polarized  light?   Purpose  of  the  problem   Revision  of  cause  of  rotation  and  optical  activity.Solutions  for  Chapter  14  –  Stereochemistry   plane   of   the   page   it   is   easy   to   see   that   neither   ring   is   a   plane   of   symmetry  for  the  other  because  of  the  oxygen  atoms.     PROBLEM  3   Cinderella’s  glass  slipper  was  undoubtedly  a  chiral  object.   We   can’t   change   the   first.   If   we   halve   the   concentration.   or   +186.   Suggested  solution   Check   the   equation   (p.   That   is   not   quite   good   enough   as   the   last   two   figures   are   the   same.   but   the   third   is   easiest   to   change.  how  could  you  tell   if  this  was  actually  +12  or  really  –348  or  +372?   Purpose  of  the  problem   Revision  of  the  meaning  of  optical  rotation  and  what  it  depends  on.   Suggested  solution   No.   and   the   concentration   of   the   solution.   –174.  Only  the  molecular   structure   matters   as   light   interacts   with   electrons   in   the   molecules.   310   on   the   textbook)   that   states   that   rotation   depends   on   three   things:   the   rotating   power   of   the   molecule.     3   .   The   molecules  of  Cinderella’s  left  foot  are  the  same  as  those  in  her  right  foot.   but   any   other   change   of   concentration  will  distinguish  them.   we   may   be   able   to   change   the   second.   Glass  is  not  chiral  (it  is  usually  made  up  of  inorganic  borosilicates).   despite  both  feet  being  macroscopically  enantiomeric.   O O O O O O   PROBLEM  2   If  a  solution  of  a  compound  has  an  optical  rotation  of  +12.  The  macroscopic  shape  of  an  object  is  irrelevant.

   Only  one  enantiomer  is  shown  here.   and   stating   whether  they  are  chiral  or  not.  Then  it  is  easy  to  say  if   each  diastereoisomer  is  chiral  or  not.4   Solutions  Manual  to  accompany  Organic  Chemistry  2e     PROBLEM  4   Discuss  the  stereochemistry  of  these  compounds.   The   one  with  the  trans  ring  junction  has  no  plane  of  symmetry  and  is  chiral   (it  has  C2  symmetry).  Both  the  cis  compound  and  the  trans  compound  can  exist  as   two  enantiomers.   O O O O   Purpose  of  the  problem   Making   sure   you   can   handle   this   important   approach   to   the   stereochemistry  of  molecules.   Suggested  solution   Just   follow   the   hint   in   the   question!   Diastereoisomers   are   different   compounds  so  they  must  be  distinguished  first.   We   can   have   two   diastereoisomers   and   neither   has   a   plane   of   symmetry.   drawing   clear   diagrams   of   each.  The  first  two  are  simple:   O one compound no diastereoisomers plane of symmetry not chiral one compound O no diastereoisomers no plane of symmetry: chiral H    The   third   structure   could   exist   as   two   diastereoisomers.  Hint:  this  means  saying  how   many   diastereoisomers   there   are.     .   not chiral chiral H plane of symmetry O O O H H H H no plane of symmetry H C2 axis of symmetry   The  last  compound  is  most  complicated  as  it  has  no  symmetry  at  all.   The   one   with   the   cis   ring   junction   has   a   plane   of   symmetry   and   is   not   chiral.

    In  the  first  reaction  the  starting  material  is  achiral  as  the  two  CH2OH   side   chains   are   identical.   with   explanations.   Suggested  solution   We   need   a   mechanism   for   each   reaction.   a   stereochemical   description   for   each   starting   material   (achiral.   chiral?   enantiomerically   enriched?)   and   an   analysis   of   what   happens   to   the   stereochemistry   in   each   reaction.Solutions  for  Chapter  14  –  Stereochemistry   H H H O H O H O H O H H enantiomers of the trans compound   enantiomers of the cis compound PROBLEM  5   In   each   case   state.   so   is   the   product.   The   product   is   chiral   as   it   has   no   plane   of   symmetry  but  it  cannot  be  one  enantiomer  as  that  would  require  one  of     5   .  Don’t  forget:  you  can’t  get  single  enantiomers  out  of  nothing  –   if   everything   that   goes   into   a   reaction   is   racemic   or   achiral.   HO CO2H HO H O O HO biological reduction O CO2Et CO2Et enzyme O NH2 HO2C OH heat NH CO2H CO2H S-(+)-glutamic acid O Ph (±) OH LiAlH4 O aqueous work-up Ph OH   Purpose  of  the  problem   Combining  mechanism  and  stereochemical  analysis  for  the  first  time.   whether   the   products   of   these   reactions  are  chiral  and/or  enantiomericaly  pure.

 because  it  is  made  up  of  enantiomerically   pure   compnents   (amino   acids).  and  with  a  fair   degree  of  heating  (the  product  is   known  trivially  as  ‘pyroglutamic   acid’)  the  amide-­‐forming  reaction   is  all  right.6   Solutions  Manual  to  accompany  Organic  Chemistry  2e   the   CH2OH   side   chains   to   cyclise   rather   than   the   other.     In   the   third   reaction.     O Ph (±) H O O AlH3 H Ph AlH3 + 2 x H+ O Ph OH OH   PROBLEM  6   This  compound  racemizes  in  base.   The   answer   is   nothing   as   the   reaction   takes   place   between   the   amine   and   the   carboxylic   acid.   can   deliver   hydride   to   one   side   of   the   ketone  only.  the  product  would  be  chiral   but  racemic.  Why  is  that?   O HO O H   Purpose  of  the  problem   To   draw   your   attention   to   the   dangers   in   working   with   nearly   symmetrical   molecules   and   revision   of   ester   exchange   (textbook   p.  We  expect  the  product  to  be  enantiomerically  enriched.  So  we  need  to  ask  what  happens  to  the  chiral  centre   during   the   reaction.   the   starting   material   is   one   enantiomer   of   a   chiral  compound.     O OH2 OH OH HO NH2 HO NH NH CO2H CO2H CO2H O NH CO2H   The  final  problem  is  a  bit  of  a  trick.   It   must   be   racemic.    But  in   this  case  the  reaction  is   intramolecular.   209).  but   racemic   while   the   product   is   achiral   as   the   two   CH2CH2OH   side   chains   are   identical   so   there   can   be   a   plane   of   symmetry   between   them.  The  starting  material  is  chiral.  207  of  the  textbook).   OH OH OH2 H OH O O O OH   O The  starting  material  for  the  second  reaction  is  planar  and  achiral.   The   product   is   a   single   enantiomer  too.  If   the  reagent  had  been  sodium  borohydride.     The   mechanism  doesn’t  really  matter  but  we  might  as  well  draw  it.   OH OH OH O OH H OH ■  Amides  don’t  usually  form    well   from  amines  and  carboxylic  acids   (see  p.     .  But  an  enzyme.

  Loss   of   the   right   hand  leaving  group  gives  one  enantiomer  of  the  ester  and  loss  of  the  left   hand  leaving  group  gives  the  other.   H O O O O O O O O O H B H H H H = O O O H       7   .Solutions  for  Chapter  14  –  Stereochemistry   Suggested  solution   Ester  exchange  in  base  goes  in  this  case  through  a  symmetrical  (achiral)   tetrahedral   intermediate   with   a   plane   of   symmetry.