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    Carbenes Nitrenes

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    Manish Kaushal
    The document discusses carbenes and nitrenes, including their structures, generation, and reactivity. Carbenes are divalent carbon species that exist in both singlet and triplet states. They can be generated through various methods and undergo reactions like cyclopropanation, insertion, and combination with nucleophiles. Nitrenes are analogous to carbenes but with nitrogen and prefer the triplet state. Transition metal carbene complexes and N-heterocyclic carbenes are also discussed as more stable derivatives. Nitrenes are generated from elimination or decomposition of azides and react through insertion into bonds.

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    Carbenes Nitrenes

    Uploaded by

    Manish Kaushal
    406 views29 pages
    The document discusses carbenes and nitrenes, including their structures, generation, and reactivity. Carbenes are divalent carbon species that exist in both singlet and triplet states. They can be generated through various methods and undergo reactions like cyclopropanation, insertion, and combination with nucleophiles. Nitrenes are analogous to carbenes but with nitrogen and prefer the triplet state. Transition metal carbene complexes and N-heterocyclic carbenes are also discussed as more stable derivatives. Nitrenes are generated from elimination or decomposition of azides and react through insertion into bonds.

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    Carbenes Nitrenes

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    The document discusses carbenes and nitrenes, including their structures, generation, and reactivity. Carbenes are divalent carbon species that exist in both singlet and triplet states. They can be generated through various methods and undergo reactions like cyclopropanation, insertion, and combination with nucleophiles. Nitrenes are analogous to carbenes but with nitrogen and prefer the triplet state. Transition metal carbene complexes and N-heterocyclic carbenes are also discussed as more stable derivatives. Nitrenes are generated from elimination or decomposition of azides and react through insertion into bonds.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    406 views29 pages

    Carbenes Nitrenes

    Uploaded by

    Manish Kaushal
    The document discusses carbenes and nitrenes, including their structures, generation, and reactivity. Carbenes are divalent carbon species that exist in both singlet and triplet states. They can be generated through various methods and undergo reactions like cyclopropanation, insertion, and combination with nucleophiles. Nitrenes are analogous to carbenes but with nitrogen and prefer the triplet state. Transition metal carbene complexes and N-heterocyclic carbenes are also discussed as more stable derivatives. Nitrenes are generated from elimination or decomposition of azides and react through insertion into bonds.

    Copyright:

    © All Rights Reserved
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    of 29

    Carbenes

     and  Nitrenes:  
    Structure,  genera3on  and  reac3vity
    Carbenes
    Review  of  carbon  valencies  and  hybridiza4on

    “Carbenes  are  neutral,  highly  reac4ve  species  containing  a  divalent  carbon  atom  with  an  electron  sextet”
    Comparison  between  triplet  and  singlet  carbenes

    Spin  state

    Geometry
    From  X-­‐ray  structures  we  know  that  both  singlet  and  triplet  states  are  bent.
    Genera3on  and  reac3vity  differences  of  singlet  vs  triplet  carbenes

    Wuth  light: Triplet  carbene


    With  gentle  warming:   singlet  cerbene    
    With  metals  (catalyst)  like  Rh(II)  or  Cu(II): Carbenoids  (similar  to  singlet  carbene)
    Carbenoids:  are  compounds  that  react  like  carbenes  but  are  not  true  divalent  C  species
    Reac3ons  of  Carbenes  and  Carbenoids
    No  maLer  how  they  are  generated,  four  typical  reac4ons

    Cyclopropana3on

    Simmons-­‐Smith
    Inser3on  into  a  C-­‐H    

    Inser7on  into  a  O–H  &  N-­‐H  


    Combina3on  with  a  nucleophile  (that  have  a  reac3ve  lone  pairs)

    Ylide  Forma4on
    The  fourth  typical  reac3on  of  carbenes  is  a  1,2-­‐shiI  (Rearrangements)
    A  group  on  the  adjacent  C  migrates  to  the  carbene  C  with  its  pair  of  electrons,  giving  an  alkene.
    The  1,2-­‐  shiS  severely  limits  the  usefulness  of  many  subs4tuted  carbenes.

    Wolff  Rearrangement
    Arndt-­‐Eistert  β-­‐amino  acid  synthesis
    Alkyne  synthesis
    Corey-­‐Fuchs  reac4on
    Seyferth-­‐Gilbert  Homologa4on
    Carbenoids  (metal  stabilized  carbenes)  described  oIen  as  M=CR2
    A  transi4on  metal  carbene  complex  is  an  organometallic  compound  featuring  a  divalent  organic  ligand.

    Reflec4ng  the  growth  of  the  area,  carbene  complexes  are  now  known  with  a  broad  range  of  different  reac4vi4es  and  
    diverse  subs4tuents..

    The  Fischer  carbenes  named  aSer  Ernst  OLo  Fischer  feature  strong  π-­‐acceptors  at  the  metal  and  being  electrophilic  at  the  
    carbene  carbon  atom.  
    Schrock  carbenes,  named  aSer  Richard  R.  Schrock,  are  characterized  by  more  nucleophilic  carbene  carbon  centers,  these  
    species  typically  feature  higher  valent  metals.  

    OSen  it  is  not  possible  to  classify  a  carbene  complex  with  regards  to  its  electrophilicity  or  nucleophilicity
    Proper3es

    Improved  thermodynamic  and  kine4c  stability  with  respect  to  the  non-­‐stabilized
    carbenes.

    Fischer  carbenes  can  be  likened  to  ketones,  with  the  carbene  carbon  being  electrophilic,  much  like  the  carbonyl  carbon  of  a  ketone.  
    Infact,  Fischer  carbene  species  can  undergo  Aldol-­‐like  reac4ons,  the  hydrogen  atoms  aLached  to  the  carbon  α  to  the  carbene  carbon  are  acidic,
    and  can  be  deprotonated  by  a  base  such  as  n-­‐butyllithium,    to  give  a  nucleophile  which  can  undergo  further  reac4on.

    Shrock  carbenes  the  bonds  are  polarized  towards  carbon  and  therefore  the  carbene  atom  is  a  nucleophile,  much  like  organometallic  cmp-­‐
    Genera4on
    Then,  N-­‐heterocyclic  carbenes  (NHCs)  already  seen.

    The  first  applica4ons  of  thiazolydenes  in  umpolung  organocatalysis  were  reported  as
    early  as  1943  (J.  Pharm.  Soc.  Jpn.  1943,  63,  296)  and  metal  complexes  of  NHCs  were
    already  reported  in  the  late  60’s.  However,  it  is  only  in  the  last  two  decades  (milestone:
    1991,  Arduengo,  first  X-­‐ray  structure  of  a  carbene)  that  NHCs  have  become  ubiquitous
    both  as  ligands  in  organometallic  chemistry  and  as  organocatalysts.
    NHCs  are  singlet  carbenes
    For  NHCs  the  singlet  state  is  lower  in  energy  than  the  triplet  state,  the  reason  being  π-­‐
    dona4on  into  the  porbitalof  carbon  from  the  heteroatoms  adjacent  to  the  carbene.

    Examples  of  the  most  frequent  NHCs  and  their  nomenclature

    R  can  be  modified  to  fine-­‐tune  the  chemical  behavior  of  the  NHC  (R  =  alkyl  or  aryl).
    Proper4es

    NHC  are  electron  rich  and  par4cularly  stable  carbenes.  The  stability  arises  both  from:
    -­‐shielding  effect  by  sterically  demanding  subs4tuents  (minor  effect);
    -­‐        electronic  stabiliza3on  (mesomeric  interac4on  of  the  lone  pairs  of  electrons  on
    the  nitrogen  atoms
    with  the  empty  p  orbital  of  the  sp2  hybridized  carbene).

    Acidic  proton:  the  pKa  value  of  the  2-­‐posi4on  of  imidazolium  salts  ranges  from  16
    to  23  (in  DMSO).
    Synthesis  (genera4on)
    Use  as  ligands
    NHC-­‐complexes  are  known  for  almost  every  transi4on  metal,  but  the  most  important  for
    organic  chemist  are:

    NHC   behave   like   phosphines   when   they   are   coordinated   to   metals   (electron   dona4ng
    proper4es)   but   they   have   more   influence   on   the   coordina4on   sphere   of   the   metal
    (sterics).
    Nitrenes
    Structure  &  hybridiza3on
    Nitrenes  are  nitrogen  analogues  of  carbenes.  The  nitrogen  atom  possesses  only  six
    valence  electrons;  in  nitrenes  the  triplet  state  is  lower  in  energy  than  the  singlet  state.

    Genera3on
    From  1,1-­‐elemina4on

    From  azides

    Main  reac4ons:  rearrangements


    Rearrangements

    Hoffman  rearrangement
    Cur4us  rearrangement
    Lossen  rearrangement
    Beckmann  rearrangement

    Industrial  nylon  synthesis


    Schmidt  Reac4on
    Mechanis4c  analogy  to  Baeyer-­‐Villiger  reac4on
    Metal  catalyzed  C–H  inser3on

    Azidinita4on???

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