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Organocatalysts which display secondary [[amine]] functionality can be described as performing either [[enamine]] catalysis (by forming catalytic quantities of an active enamine nucleophile) or [[imine|iminium]] catalysis (by forming catalytic quantities of an activated iminium electrophile).
Organocatalysts which display secondary [[amine]] functionality can be described as performing either [[enamine]] catalysis (by forming catalytic quantities of an active enamine nucleophile) or [[imine|iminium]] catalysis (by forming catalytic quantities of an activated iminium electrophile).

==Applications==
{{sectstub}}


==Examples==
==Examples==
A commonly described organocatalyst is the naturally occurring amino acid, L-[[proline]], which can facilitate [[aldol reaction]]s. Many synthetic organocatalysts have been made based on the proline model.
A commonly described organocatalyst is the naturally occurring amino acid, L-[[proline]], which can facilitate [[aldol reaction]]s. Many synthetic organocatalysts have been made based on the proline model.


⚫
== Non-covalent organocatalysis ==
⚫
In Nature non-covalent interactions such as hydrogen bonging play a crucial role in in enzyme catalysis that is charcaterized by effective substrate recognition (molecular recognition), substrate activation, and enormous accelation of organic tranformations.
==See also==
==See also==
{{chiral synthesis}}
{{chiral synthesis}}

==External links==
⚫
*For additional information and scientific communication on this ongoing research field see:[http://www.chemie.uni-giessen.de/proj/det/schreiner/19/]


==References==
==References==
* {{cite book | title=Asymmetric Organocatalysis| last=Berkessel, A., Groeger, H.| date=2005| publisher=Wiley-VCH| location=Weinheim| id=ISBN 3-527-30517-3}}
* {{cite book | title=Asymmetric Organocatalysis| last=Berkessel, A., Groeger, H.| date=2005| publisher=Wiley-VCH| location=Weinheim| id=ISBN 3-527-30517-3}}
⚫
*'''Selected puplications on non-covalent organocatalysis through double hydrogen-bonding thiourea derivatives'''
⚫
* [1] Alexander Wittkopp, Peter R. Schreiner, "Diels-Alder Reactions in Water and in Hydrogen-Bonding Environments", book chapter in "The Chemistry of Dienes and Polyenes" Zvi Rappoport (Ed.), Volume 2, John Wiley & Sons Inc.; Chichester, '''2000''', 1029-1088. ISBN: 0-471-72054-2. [http://www.amazon.de/Chemistry-Dienes-Polyenes-Functional-Groups/dp/0471720542/ref=sr_11_1/028-5859069-3592513?ie=UTF8&qid=1179408092&sr=11-1]
⚫
* [2] Alexander Wittkopp, "Organocatalysis of Diels-Alder Reactions by Neutral Hydrogen Bond Donors in Organic and Aqueous Solvents", dissertation written in German, Universität Göttingen, '''2001'''. english abstract/download: [http://webdoc.sub.gwdg.de/diss/2001/wittkopp/index.html]
⚫
* [3] Peter R. Schreiner, Alexander Wittkopp, "H-Bonding Additives Act Like Lewis Acid Catalysts", ''Org. Lett.'' '''2002''', ''4'', 217-220. abstract/download: [http://pubs.acs.org/cgi bin/abstract.cgi/orlef7/2002/4/i02/abs/ol017117s.html]
⚫
* [4] Alexander Wittkopp, Peter R. Schreiner,"Metal-Free, Noncovalent Catalysis of Diels-Alder Reactions by Neutral Hydrogen Bond Donors in Organic Solvents and in Water", ''Chem. Eur. J.'' '''2003''', ''9'', 407-414. abstract/download: [http://www3.interscience.wiley.com/search/allsearch?mode=viewselected&product=journal&ID=102524991&view_selected.x=0&view_selected.y=0&view_selected=view_selected]
⚫
* [5] Peter R. Schreiner, review: "Metal-free organocatalysis through explicit hydrogen bonding interactions", ''Chem. Soc. Rev.'' '''2003''', ''32'', 289-296. abstract/download:[http://www.rsc.org/Publishing/Journals/CS/article.asp?doi=b107298f]
⚫
* [6] Mike Kotke, Peter R. Schreiner,"Acid-free, organocatalytic acetalization", Tetrahedron '''2006''', ''62'', 434-439. abstract/download: [http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6THR-4HDG975-4&_user=10&_coverDate=01%2F09%2F2006&_rdoc=1&_fmt=summary&_orig=browse&_srch=UOI(B6THR4HDG9754)&_orig_alid=0&_cdi=5289&_sort=d&_docanchor=&view=c&_subId=600487&_ct=1&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=dfded621304d3c71ab403e3535959f0a]
⚫
* [7] Christian M. Kleiner, Peter R. Schreiner,"Hydrophobic amplification of noncovalent organocatalysis", ''Chem. Commun.''''' 2006''', 4315-4017.abstract/download:[http://www.rsc.org/Publishing/Journals/CC/article.asp?doi=b605850g]
⚫
* [8] Mike Kotke, Peter R. Schreiner,"Generally Applicable Organocatalytic Tetrahydropyranylation of Hydroxy Functionalities with Very Low Catalyst Loading", ''Synthesis'' '''2007''', ''5'', 779-790. abstract/download:[http://www.thieme-connect.de/ejournals/abstract/synthesis/doi/10.1055/s-2007-965917]
⚫
* [9] Lukas Wanka, Chiara Cabrele, Maksims Vanejews, Peter R. Schreiner,"γ-Aminoadamantanecarboxylic Acids Through Direct C–H Bond Amidations", ''Eur. J. Org. Chem.'' '''2007''', 1474-1490. abstract/download:[http://www3.interscience.wiley.com/cgi-bin/abstract/114110020/ABSTRACT]
⚫
* [10] Petri M. Pihko, review: "Activation of Carbonyl Compounds by Double Hydrogen Bonding: An Emerging Tool in Asymmetric Catalysis", ''Angew. Chem. Int. Ed.'' '''2004''', ''43'', 2062 –2064. download:[http://www3.interscience.wiley.com/cgi-bin/abstract/108061497/ABSTRACT]
⚫
* [11] Yoshiji Takemoto, review: "Recognition and activation by ureas and thioureas: stereoselective reactions using ureas and thioureas as hydrogen-bonding donors", ''Org. Biomol. Chem.'' '''2005''', ''3'', 4299-4306. abstract/download: [http://rsc.org/Publishing/Journals/OB/article.asp?doi=b511216h]
⚫
* [12] Mark S. Taylor, Eric N. Jacobsen, review: "Asymmetric Catalysis by Chiral Hydrogen-Bond Donors", ''Angew. Chem. Int. Ed.'' '''2006''', ''45'', 1520 – 1543. abstract/download: [http://www3.interscience.wiley.com/cgi-bin/abstract/112455892/ABSTRACT]
⚫
* [13] Stepen J. Connon, review: "Organocatalysis Mediated by (Thio)urea Derivatives", ''Chem. Eur. J.'' '''2006''', ''12'', 5418 –5427.abstract/download: [http://www3.interscience.wiley.com/cgi-bin/abstract/112470681/ABSTRACT]




{{chem-stub}}
{{chem-stub}}
[[Category:Catalysts]]
[[Category:Catalysts]]
[[Category:Organic chemistry]]
[[Category:Organic chemistry]]


⚫
== Non-covalent organocatalysis ==

⚫
In Nature non-covalent interactions such as hydrogen bonging play a crucial role in in enzyme catalysis that is charcaterized by effective substrate recognition (molecular recognition), substrate activation, and enormous accelation of organic tranformations.
Based on first exmaninations on hydrogen-bonding interactions of small, metal-free compounds with




















⚫
'''Selected puplications on non-covalent organocatalysis through double hydrogen-bonding thiourea derivatives'''

⚫
For additional information and scientific communication on this ongoing research field see: [http://www.chemie.uni-giessen.de/proj/det/schreiner/19/]

⚫
[1] Alexander Wittkopp, Peter R. Schreiner, "Diels-Alder Reactions in Water and in Hydrogen-Bonding Environments", book chapter in "The Chemistry of Dienes and Polyenes" Zvi Rappoport (Ed.), Volume 2, John Wiley & Sons Inc.; Chichester, '''2000''', 1029-1088. ISBN: 0-471-72054-2.
[http://www.amazon.de/Chemistry-Dienes-Polyenes-Functional-Groups/dp/0471720542/ref=sr_11_1/028-5859069-3592513?ie=UTF8&qid=1179408092&sr=11-1]

[2] Alexander Wittkopp, "Organocatalysis of Diels-Alder Reactions by Neutral Hydrogen Bond Donors in Organic and Aqueous Solvents",
⚫
dissertation written in German, Universität Göttingen, '''2001'''. english abstract/download: [http://webdoc.sub.gwdg.de/diss/2001/wittkopp/index.html]

⚫
[3] Peter R. Schreiner, Alexander Wittkopp, "H-Bonding Additives Act Like Lewis Acid Catalysts", ''Org. Lett.'' '''2002''', ''4'', 217-220. abstract/download: [http://pubs.acs.org/cgi-bin/abstract.cgi/orlef7/2002/4/i02/abs/ol017117s.html]

[4] Alexander Wittkopp, Peter R. Schreiner,"Metal-Free, Noncovalent Catalysis of Diels-Alder Reactions by Neutral
Hydrogen Bond Donors in Organic Solvents and in Water", ''Chem. Eur. J.'' '''2003''', ''9'', 407-414. abstract/download:
⚫
[http://www3.interscience.wiley.com/search/allsearch?mode=viewselected&product=journal&ID=102524991&view_selected.x=0&view_selected.y=0&view_selected=view_selected]

⚫
[5] Peter R. Schreiner, review: "Metal-free organocatalysis through explicit hydrogen bonding interactions", ''Chem. Soc. Rev.'' '''2003''', ''32'', 289-296. abstract/download: [http://www.rsc.org/Publishing/Journals/CS/article.asp?doi=b107298f]

[6] Mike Kotke, Peter R. Schreiner,"Acid-free, organocatalytic acetalization", Tetrahedron '''2006''', ''62'', 434-439. abstract/download:
⚫
[http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6THR-4HDG975-4&_user=10&_coverDate=01%2F09%2F2006&_rdoc=1&_fmt=summary&_orig=browse&_srch=UOI(B6THR4HDG9754)&_orig_alid=0&_cdi=5289&_sort=d&_docanchor=&view=c&_subId=600487&_ct=1&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=dfded621304d3c71ab403e3535959f0a]

[7] Christian M. Kleiner, Peter R. Schreiner,"Hydrophobic amplification of noncovalent organocatalysis", ''Chem.
⚫
Commun.''''' 2006''', 4315-4017. abstract/download: [http://www.rsc.org/Publishing/Journals/CC/article.asp?doi=b605850g]

[8] Mike Kotke, Peter R. Schreiner,"Generally Applicable Organocatalytic Tetrahydropyranylation of Hydroxy
⚫
Functionalities with Very Low Catalyst Loading", ''Synthesis'' '''2007''', ''5'', 779-790. abstract/download: [http://www.thieme-connect.de/ejournals/abstract/synthesis/doi/10.1055/s-2007-965917]

[9] Lukas Wanka, Chiara Cabrele, Maksims Vanejews, Peter R. Schreiner,"γ-Aminoadamantanecarboxylic Acids Through
⚫
Direct C–H Bond Amidations", ''Eur. J. Org. Chem.'' '''2007''', 1474-1490. abstract/download: [http://www3.interscience.wiley.com/cgi-bin/abstract/114110020/ABSTRACT]

⚫
[10] Petri M. Pihko, review: "Activation of Carbonyl Compounds by Double Hydrogen Bonding: An Emerging Tool in Asymmetric Catalysis", ''Angew. Chem. Int. Ed.'' '''2004''', ''43'', 2062 –2064. download: [http://www3.interscience.wiley.com/cgi-bin/abstract/108061497/ABSTRACT]

⚫
[11] Yoshiji Takemoto, review: "Recognition and activation by ureas and thioureas: stereoselective reactions using ureas and thioureas as hydrogen-bonding donors", ''Org. Biomol. Chem.'' '''2005''', ''3'', 4299-4306. abstract/download: [http://rsc.org/Publishing/Journals/OB/article.asp?doi=b511216h]

⚫
[12] Mark S. Taylor, Eric N. Jacobsen, review: "Asymmetric Catalysis by Chiral Hydrogen-Bond Donors", ''Angew. Chem. Int. Ed.'' '''2006''', ''45'', 1520 – 1543. abstract/download: [http://www3.interscience.wiley.com/cgi-bin/abstract/112455892/ABSTRACT]

⚫
[13] Stepen J. Connon, review: "Organocatalysis Mediated by (Thio)urea Derivatives", ''Chem. Eur. J.'' '''2006''', ''12'', 5418 –5427.
abstract/download: [http://www3.interscience.wiley.com/cgi-bin/abstract/112470681/ABSTRACT]

Revision as of 17:19, 17 May 2007

Organocatalysis is the catalysis of chemical reactions using a purely organic compound. This compound is composed of mainly carbon, hydrogen, nitrogen, sulfur, and phosphorus, and does not contain any metals.

Organocatalysts are usually small molecules. They are robust, and commercially available in quantity, making it inexpensive and readily obtained. They are stable to moisture and oxygen, making inconvenient air sensitive techniques unnecessary. Unfortunately, organocatalysts often require high loadings to be effective, and may be difficult to separate from the resultant reaction mixture.

Organocatalysts which display secondary amine functionality can be described as performing either enamine catalysis (by forming catalytic quantities of an active enamine nucleophile) or iminium catalysis (by forming catalytic quantities of an activated iminium electrophile).

Examples

A commonly described organocatalyst is the naturally occurring amino acid, L-proline, which can facilitate aldol reactions. Many synthetic organocatalysts have been made based on the proline model.

Non-covalent organocatalysis

In Nature non-covalent interactions such as hydrogen bonging play a crucial role in in enzyme catalysis that is charcaterized by effective substrate recognition (molecular recognition), substrate activation, and enormous accelation of organic tranformations.

See also

  • For additional information and scientific communication on this ongoing research field see:[1]

References

  • Berkessel, A., Groeger, H. (2005). Asymmetric Organocatalysis. Weinheim: Wiley-VCH. ISBN 3-527-30517-3.{{cite book}}: CS1 maint: multiple names: authors list (link)
  • Selected puplications on non-covalent organocatalysis through double hydrogen-bonding thiourea derivatives
  • [1] Alexander Wittkopp, Peter R. Schreiner, "Diels-Alder Reactions in Water and in Hydrogen-Bonding Environments", book chapter in "The Chemistry of Dienes and Polyenes" Zvi Rappoport (Ed.), Volume 2, John Wiley & Sons Inc.; Chichester, 2000, 1029-1088. ISBN: 0-471-72054-2. [2]
  • [2] Alexander Wittkopp, "Organocatalysis of Diels-Alder Reactions by Neutral Hydrogen Bond Donors in Organic and Aqueous Solvents", dissertation written in German, Universität Göttingen, 2001. english abstract/download: [3]
  • [3] Peter R. Schreiner, Alexander Wittkopp, "H-Bonding Additives Act Like Lewis Acid Catalysts", Org. Lett. 2002, 4, 217-220. abstract/download: bin/abstract.cgi/orlef7/2002/4/i02/abs/ol017117s.html
  • [4] Alexander Wittkopp, Peter R. Schreiner,"Metal-Free, Noncovalent Catalysis of Diels-Alder Reactions by Neutral Hydrogen Bond Donors in Organic Solvents and in Water", Chem. Eur. J. 2003, 9, 407-414. abstract/download: [4]
  • [5] Peter R. Schreiner, review: "Metal-free organocatalysis through explicit hydrogen bonding interactions", Chem. Soc. Rev. 2003, 32, 289-296. abstract/download:[5]
  • [6] Mike Kotke, Peter R. Schreiner,"Acid-free, organocatalytic acetalization", Tetrahedron 2006, 62, 434-439. abstract/download: [6]
  • [7] Christian M. Kleiner, Peter R. Schreiner,"Hydrophobic amplification of noncovalent organocatalysis", Chem. Commun. 2006, 4315-4017.abstract/download:[7]
  • [8] Mike Kotke, Peter R. Schreiner,"Generally Applicable Organocatalytic Tetrahydropyranylation of Hydroxy Functionalities with Very Low Catalyst Loading", Synthesis 2007, 5, 779-790. abstract/download:[8]
  • [9] Lukas Wanka, Chiara Cabrele, Maksims Vanejews, Peter R. Schreiner,"γ-Aminoadamantanecarboxylic Acids Through Direct C–H Bond Amidations", Eur. J. Org. Chem. 2007, 1474-1490. abstract/download:[9]
  • [10] Petri M. Pihko, review: "Activation of Carbonyl Compounds by Double Hydrogen Bonding: An Emerging Tool in Asymmetric Catalysis", Angew. Chem. Int. Ed. 2004, 43, 2062 –2064. download:[10]
  • [11] Yoshiji Takemoto, review: "Recognition and activation by ureas and thioureas: stereoselective reactions using ureas and thioureas as hydrogen-bonding donors", Org. Biomol. Chem. 2005, 3, 4299-4306. abstract/download: [11]
  • [12] Mark S. Taylor, Eric N. Jacobsen, review: "Asymmetric Catalysis by Chiral Hydrogen-Bond Donors", Angew. Chem. Int. Ed. 2006, 45, 1520 – 1543. abstract/download: [12]
  • [13] Stepen J. Connon, review: "Organocatalysis Mediated by (Thio)urea Derivatives", Chem. Eur. J. 2006, 12, 5418 –5427.abstract/download: [13]


Quelle: https://en.wikipedia.org/wiki/Special%3ADiff%2F131577228