Aza-Wittig reaction: Difference between revisions
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The mechanism of the aza-Wittig reaction is analogous to that of the [[Wittig reaction]], with the Wittig reagent replaced by an iminophosphorane.<ref name=":0" /> |
The mechanism of the aza-Wittig reaction is analogous to that of the [[Wittig reaction]], with the Wittig reagent replaced by an iminophosphorane.<ref name=":0" /> |
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The formation of the iminophosphorane from the azide begins with the attack of triphenylphosphine on the terminal nitrogen atom. The intermediate loses nitrogen via a four-membered ring transition state.<ref name=":0" /> |
The formation of the iminophosphorane from the azide begins with the attack of [[triphenylphosphine]] on the terminal nitrogen atom. The intermediate loses nitrogen via a four-membered ring transition state.<ref name=":0" /> |
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==Scope and limitations== |
==Scope and limitations== |
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There exists solid-supported modifications of the reaction.<ref>{{Cite journal |last=Hemming |first=Karl |last2=Bevan |first2=Matthew J. |last3=Loukou |first3=Christina |last4=Patel |first4=Snahal D. |last5=Renaudeau |first5=Denis |date=2001-02-20 |title=ChemInform Abstract: A One‐Pot Aza‐Wittig Based Solution and Polymer‐Supported Route to Amines. |url=https://onlinelibrary.wiley.com/doi/10.1002/chin.200108116 |journal=ChemInform |language=en |volume=32 |issue=8 |doi=10.1002/chin.200108116 |issn=0931-7597}}</ref><ref name=":0" /><ref name=":2">{{Cite journal |last=Lao |first=Zhiqi |last2=Toy |first2=Patrick H |date=2016-11-30 |title=Catalytic Wittig and aza-Wittig reactions |url=http://dx.doi.org/10.3762/bjoc.12.253 |journal=Beilstein Journal of Organic Chemistry |volume=12 |pages=2577–2587 |doi=10.3762/bjoc.12.253 |issn=1860-5397}}</ref> |
There exists solid-supported modifications of the reaction.<ref>{{Cite journal |last=Hemming |first=Karl |last2=Bevan |first2=Matthew J. |last3=Loukou |first3=Christina |last4=Patel |first4=Snahal D. |last5=Renaudeau |first5=Denis |date=2001-02-20 |title=ChemInform Abstract: A One‐Pot Aza‐Wittig Based Solution and Polymer‐Supported Route to Amines. |url=https://onlinelibrary.wiley.com/doi/10.1002/chin.200108116 |journal=ChemInform |language=en |volume=32 |issue=8 |doi=10.1002/chin.200108116 |issn=0931-7597}}</ref><ref name=":0" /><ref name=":2">{{Cite journal |last=Lao |first=Zhiqi |last2=Toy |first2=Patrick H |date=2016-11-30 |title=Catalytic Wittig and aza-Wittig reactions |url=http://dx.doi.org/10.3762/bjoc.12.253 |journal=Beilstein Journal of Organic Chemistry |volume=12 |pages=2577–2587 |doi=10.3762/bjoc.12.253 |issn=1860-5397}}</ref> |
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Similar to the |
Similar to the Wittig reaction, the reaction suffers from issues with [[triphenylphosphine oxide]] by-product removal. Such an issue is mitigated via catalytic aza-Wittig-reactions, some of which entail elements other than phosphorus, like [[arsenic]] and [[tellurium]]<ref name=":2" /><ref>{{Cite journal |last=Li |first=Huaifeng |last2=Lupp |first2=Daniel |last3=Das |first3=Pradip K. |last4=Yang |first4=Li |last5=Gonçalves |first5=Théo P. |last6=Huang |first6=Mei-Hui |last7=El Hajoui |first7=Marwa |last8=Liang |first8=Lan-Chang |last9=Huang |first9=Kuo-Wei |date=2021-04-02 |title=Redox-Neutral Imination of Alcohol with Azide: A Sustainable Alternative to the Staudinger/Aza-Wittig Reaction |url=https://pubs.acs.org/doi/10.1021/acscatal.1c00379 |journal=ACS Catalysis |language=en |volume=11 |issue=7 |pages=4071–4076 |doi=10.1021/acscatal.1c00379 |issn=2155-5435}}</ref>.{{clear}} |
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==History== |
==History== |
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The reagent for the aza-Wittig reaction, iminophosphorane, |
The reagent for the aza-Wittig reaction, iminophosphorane, was discovered in 1919 by [[Hermann Staudinger]]. The reaction itself was discovered thirty years later.<ref name=":1">{{Cite web |title=Aza-Wittig Reaction |url=https://en.chem-station.com/reactions-2/2015/03/aza-wittig-reaction.html |access-date=2024-05-24 |language=en-US}}</ref> |
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==See also== |
==See also== |
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*[[Staudinger reaction]] |
*[[Staudinger reaction]] |
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*[[Wittig reaction]] |
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*[[Schiff base]] |
*[[Schiff base]] |
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Revision as of 15:39, 24 May 2024
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The Aza-Wittig reaction or is a chemical reaction of a carbonyl group with an aza-ylide, also known as an iminophosphorane. Aza-Wittig reactions are most commonly used to convert aldehydes and ketones to imines, which may be further reduced to yield secondary amines.[1] Aza-ylides can be obtained via the reaction of a trialkylphosphine and an organic azide with the loss of dinitrogen, with triphenylphosphine being the most commonly used. For substrates with both an azide and a carbonyl group, intramolecular coupling can be achieved.[2]
Reaction mechanism
The mechanism of the aza-Wittig reaction is analogous to that of the Wittig reaction, with the Wittig reagent replaced by an iminophosphorane.[1]
The formation of the iminophosphorane from the azide begins with the attack of triphenylphosphine on the terminal nitrogen atom. The intermediate loses nitrogen via a four-membered ring transition state.[1]
Scope and limitations
Besides preparing imines from aldehydes and ketones, the aza-Wittig-reaction can also convert carbon dioxide to isocyanates, carbon disulfide to organic thiocyanates, and isocyanates to carbodiimides.[1][3]
There exists solid-supported modifications of the reaction.[4][1][5]
Similar to the Wittig reaction, the reaction suffers from issues with triphenylphosphine oxide by-product removal. Such an issue is mitigated via catalytic aza-Wittig-reactions, some of which entail elements other than phosphorus, like arsenic and tellurium[5][6].
History
The reagent for the aza-Wittig reaction, iminophosphorane, was discovered in 1919 by Hermann Staudinger. The reaction itself was discovered thirty years later.[3]
See also
References
- ^ a b c d e Kurti 1 Czako 2, Laszlo 1 Barbara 2. Strategic Applications of Named Reactions in Organic Synthesis. Elsevier. pp. 24–25. ISBN 0-12-429785-4.
{{cite book}}: CS1 maint: numeric names: authors list (link) - ^ Wamhoff, Heinrich; Richardt, Gabriele; Stölben, Stephan (1995-01-01), Katritzky, Alan R. (ed.), "Iminophosphoranes: Versatile Tools in Heterocyclic Synthesis", Advances in Heterocyclic Chemistry, vol. 64, Academic Press, pp. 159–249, doi:10.1016/s0065-2725(08)60172-5, retrieved 2024-05-24
- ^ a b "Aza-Wittig Reaction". Retrieved 2024-05-24.
- ^ Hemming, Karl; Bevan, Matthew J.; Loukou, Christina; Patel, Snahal D.; Renaudeau, Denis (2001-02-20). "ChemInform Abstract: A One‐Pot Aza‐Wittig Based Solution and Polymer‐Supported Route to Amines". ChemInform. 32 (8). doi:10.1002/chin.200108116. ISSN 0931-7597.
- ^ a b Lao, Zhiqi; Toy, Patrick H (2016-11-30). "Catalytic Wittig and aza-Wittig reactions". Beilstein Journal of Organic Chemistry. 12: 2577–2587. doi:10.3762/bjoc.12.253. ISSN 1860-5397.
- ^ Li, Huaifeng; Lupp, Daniel; Das, Pradip K.; Yang, Li; Gonçalves, Théo P.; Huang, Mei-Hui; El Hajoui, Marwa; Liang, Lan-Chang; Huang, Kuo-Wei (2021-04-02). "Redox-Neutral Imination of Alcohol with Azide: A Sustainable Alternative to the Staudinger/Aza-Wittig Reaction". ACS Catalysis. 11 (7): 4071–4076. doi:10.1021/acscatal.1c00379. ISSN 2155-5435.
External links
- Wittig reaction in Organic Syntheses, Coll. Vol. 10, p. 703 (2004); Vol. 75, p. 153 (1998). (Article)
- Wittig reaction in Organic Syntheses, Coll. Vol. 5, p. 361 (1973); Vol. 45, p. 33 (1965). (Article)