Kabachnik–Fields reaction: Difference between revisions
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{{Short description|Chemical reaction}} |
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The '''Kabachnik–Fields reaction''' is an [[organic reaction]] forming an α-[[amino]] [[phosphonate]] from an [[amine]], a [[carbonyl]] compound and a dialkyl phosphonate. Aminophosphonates are synthetic targets of some importance as [[phosphorus]] analogues of α-[[amino acid]]s (a [[bioisosterism|bioisostere]]). This [[multicomponent reaction]] was independently discovered by [[Martin Izrailevich Kabachnik]]<ref>{{cite journal| last=Kabachnik | first=Martin I. |author2=T. Ya. Medved | year=1952 | title=Новый метод синтеза сс-аминофосфиновых кислот | trans_title=<!-- A new method for the synthesis of α-amino ? acids --> | journal=[[Doklady Akademii Nauk SSSR]] | volume=83 | page=689}}</ref> and [[Ellis K. Fields]]<ref>{{cite journal| last=Fields | first=Ellis K. | year=1952 | title=The synthesis of esters of substituted amino phosphonic acids | journal=[[Journal of the American Chemical Society]] | volume=74 | issue=6 | pages=1528–1531 | doi=10.1021/ja01126a054}}</ref> in 1952. |
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In [[organophosphorus chemistry]], the '''Kabachnik–Fields reaction''' is a three-component [[organic reaction]] forming [[aminophosphonate|α-aminomethylphosphonates]] from an [[amine]], a [[carbonyl compound]], and a [[phosphite ester|dialkyl phosphonate]], (RO)<sub>2</sub>P(O)H (that are also called dialkylphosphites).<ref>{{cite journal|title=The Kabachnik-Fields reaction: mechanism and synthetic use|author1=Keglevich, Gyorgy |author2=Balint, Erika |journal=Molecules|year=2012|volume=17|issue=11|pages=12821–12835|doi=10.3390/molecules171112821|pmid=23117425|pmc=6268146|doi-access=free}}</ref> Aminophosphonates are synthetic targets of some importance as [[phosphorus]] [[analog (chemistry)|analogues]] of α-[[amino acid]]s (a [[bioisosterism|bioisostere]]). This [[multicomponent reaction]] was independently discovered by {{ill|Martin Kabachnik|ru|Кабачник, Мартин Израилевич}}<ref>{{cite journal |last1=Kabachnik |first1=Martin I. |last2=Medved |first2=T. Ya. |year=1953 |title=New method for the synthesis of 1-aminoalkylphosphonic acids Communication 1 |trans-title= |url=https://doi.org/10.1007/BF01178856 |journal=[[Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science]] |language=English |volume=2 |issue=5 |pages=769–777|doi=10.1007/BF01178856 }}</ref><ref>{{Cite journal |last1=Medved |first1=T. Ya. |last2=Kabachnik |first2=Martin I. |year=1954 |title=New method for the synthesis of amino-phosphonic acids. Communication 2. Reaction of ketones with dialkyl phosphites and ammonia |url=https://doi.org/10.1007/BF01177621 |journal=[[Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science]] |volume=3 |issue=2 |pages=255–261|doi=10.1007/BF01177621 }}</ref> and Ellis K. Fields<ref>{{cite journal| last=Fields | first=Ellis K. | year=1952 | title=The synthesis of esters of substituted amino phosphonic acids | journal=[[Journal of the American Chemical Society]] | volume=74 | issue=6 | pages=1528–1531 | doi=10.1021/ja01126a054}}</ref> in 1952. The reaction is very similar to the two-component [[Pudovik reaction]], which involves condensation of the phosphite and a preformed [[imine]]. |
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:[[Image:Kabachnik-Fields Reaction.svg|Kabachnik-Fields |
:[[Image:Kabachnik-Fields Reaction.svg|Kabachnik-Fields reaction]] |
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The first step in this reaction is the formation of an [[imine]] followed by |
The first step in this reaction is the formation of an [[imine]], followed by a [[hydrophosphonylation]] step where the phosphonate P-H bond across the C=N double bond.<ref>{{cite journal| last=Zefirov | first=Nikolay S. |author2=Elena D. Matveeva | date=2008-01-18 | title=Catalytic Kabachnik-Fields reaction: New horizons for old reaction | journal=[[Arkivoc]] | volume=2008 | issue=i | pages=1–17 | url=http://www.arkat-usa.org/get-file/22930/?wikipedia-format=.pdf | accessdate=2009-12-08 | doi=10.3998/ark.5550190.0009.101| doi-access=free}}</ref> The starting carbonyl component is usually an [[aldehyde]] and sometimes a [[ketone]]. The reaction can be accelerated with a combination of dehydrating reagent and [[Lewis acid]]. |
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Enantioselective variants of the Kabachnik-Fields reaction have been developed, for example employing α-methylbenzylamine provides a chiral, non-racemic α-aminophosphonate.<ref>{{cite journal|author1=Gilmore, F. |author2=McBride, A. |journal=J. Am. Chem. Soc.|year=1972|volume=94|pages= 4361|doi=10.1021/ja00767a065|pmid=5036657|title=Synthesis of an optically active -aminophosphonic acid|issue=12}}</ref> |
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The reaction is accelerated with a combination of dehydrating reagent and [[Lewis acid]]. The carbonyl component in the reaction is usually an [[aldehyde]] and sometimes a [[ketone]]. |
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:[[File:PhosAddEnant2.png]] |
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==References== |
==References== |
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{{DEFAULTSORT:Kabachnik-Fields reaction}} |
{{DEFAULTSORT:Kabachnik-Fields reaction}} |
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[[Category:Multiple component reactions]] |
[[Category:Multiple component reactions]] |
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Latest revision as of 22:26, 27 September 2024
In organophosphorus chemistry, the Kabachnik–Fields reaction is a three-component organic reaction forming α-aminomethylphosphonates from an amine, a carbonyl compound, and a dialkyl phosphonate, (RO)2P(O)H (that are also called dialkylphosphites).[1] Aminophosphonates are synthetic targets of some importance as phosphorus analogues of α-amino acids (a bioisostere). This multicomponent reaction was independently discovered by Martin Kabachnik[2][3] and Ellis K. Fields[4] in 1952. The reaction is very similar to the two-component Pudovik reaction, which involves condensation of the phosphite and a preformed imine.
The first step in this reaction is the formation of an imine, followed by a hydrophosphonylation step where the phosphonate P-H bond across the C=N double bond.[5] The starting carbonyl component is usually an aldehyde and sometimes a ketone. The reaction can be accelerated with a combination of dehydrating reagent and Lewis acid.
Enantioselective variants of the Kabachnik-Fields reaction have been developed, for example employing α-methylbenzylamine provides a chiral, non-racemic α-aminophosphonate.[6]
References
[edit]- ^ Keglevich, Gyorgy; Balint, Erika (2012). "The Kabachnik-Fields reaction: mechanism and synthetic use". Molecules. 17 (11): 12821–12835. doi:10.3390/molecules171112821. PMC 6268146. PMID 23117425.
- ^ Kabachnik, Martin I.; Medved, T. Ya. (1953). "New method for the synthesis of 1-aminoalkylphosphonic acids Communication 1". Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science. 2 (5): 769–777. doi:10.1007/BF01178856.
- ^ Medved, T. Ya.; Kabachnik, Martin I. (1954). "New method for the synthesis of amino-phosphonic acids. Communication 2. Reaction of ketones with dialkyl phosphites and ammonia". Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science. 3 (2): 255–261. doi:10.1007/BF01177621.
- ^ Fields, Ellis K. (1952). "The synthesis of esters of substituted amino phosphonic acids". Journal of the American Chemical Society. 74 (6): 1528–1531. doi:10.1021/ja01126a054.
- ^ Zefirov, Nikolay S.; Elena D. Matveeva (2008-01-18). "Catalytic Kabachnik-Fields reaction: New horizons for old reaction" (PDF). Arkivoc. 2008 (i): 1–17. doi:10.3998/ark.5550190.0009.101. Retrieved 2009-12-08.
- ^ Gilmore, F.; McBride, A. (1972). "Synthesis of an optically active -aminophosphonic acid". J. Am. Chem. Soc. 94 (12): 4361. doi:10.1021/ja00767a065. PMID 5036657.