An Efficient Synthesis of Novel α‐Aminophosphonates Based on a Mannich‐Type Reaction

Risch, Nikolaus; Piper, Stefan; Winter, Andreas; Lefarth‐Risse, Annette

doi:10.1002/ejoc.200400618

Cited by 12 publications

(16 citation statements)

References 59 publications

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“…Therefore, the search for efficient precursors for the synthesis of carboxylic acids 235 from carbonyl compounds by the Horner reaction has continued. From the mid-1970s to the early 1980s, many acetal-like derivatives of diethyl formylphosphonates 13 – 32 [18,19,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56], where the negative charge of the carbanion was stabilized by two heteroatoms of the “acetal” group, were obtained [54]. See also Figure 2, where R = OEt.…”

Section: General Chemical Properties Of Phosphorylated Formaldehydmentioning

confidence: 99%

“…This scheme is currently used [33,165]; phosphorus trichloride can be used instead of thionyl chloride [83]. Dimethyl [( N,N -dimethylamino)chloromethyl]phosphonate ( 172 ) was found to undergo spontaneous dealkylation on storage [31], therefore only diethyl [( N,N -dimethylamino)chloromethyl]phosphonate ( 173 ) is used in organic synthesis.…”

Section: Phosphorylated Formaldehyde Halogenoaminals (Phosphorylatmentioning

confidence: 99%

“…Compound 173 reacts with methyl aryl ketones [30] and dialkyl or aryl alkyl ketones [33] to give diethyl [( N,N -dimethylamino)(aroyl(or alkanoyl)alkylmethyl)methyl]phosphonates 292 and 293 [30,33], phosphorylated analogs of natural α-amino acids potentially possessing biological activity [33] (Scheme 97). However, reaction stereoselectivity is low, and the anti / syn ratio is 2:1.…”

Section: Phosphorylated Formaldehyde Halogenoaminals (Phosphorylatmentioning

confidence: 99%

“…However, many authors showed that formylphosphinoyl compounds are also stable in the form of formylphosphonic acid ( 12 ) [12,14,15], its disodium salt [15], aldehyde group derivatives such as acetals 13 [18,19,20] and structurally related compounds. These compounds are thioacetals 14 [21,22,23], aminonitriles 15 [24,25,26], diphosphinoyl ( N,N -dialkylaminomethyl)methanes 16 [27,28,29], chloro(or bromo)aminals 17 [30,31,32,33,34], mixed S,O-thioacetals 18 [35,36,37], aminals 19 [30,38], aminoacetals 20 [31,32,38,39], aminothioacetals 21 [32], chloroacetals 22 [40,41], chloro- (or bromo-) thioacetals 23 [40,42,43], α-chlorosulfinyl derivatives 24 [44,45], α-alkoxynitriles 25 [46,47,48], α-thionitriles 26 [46], α-dihalo derivatives 27 [49,50,51], α-alkoxydiphosphoryl compounds 28 [41], α-mercaptodiphosphoryl compounds 29 [40,52,53], α-alkoxysilyl derivatives 30 [54], α-aminosilyl derivatives 31 [29,55], or α-mercaptosilyl derivatives 32 [56] (Figure 2):…”

Section: Introductionmentioning

confidence: 99%

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Chemistry of Phosphorylated Formaldehyde Derivatives. Part I

Morgalyuk

2014

Molecules

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Abstract:The underinvestigated derivatives of unstable phosphorylated formaldehyde acetals and some of the structurally related compounds, such as thioacetals, aminonitriles, aminomethylphosphinoyl compounds, are considered. Separately considered are halogen aminals of phosphorylated formaldehyde, acetals of phosphorylated formaldehyde of H-phosphinate-type and a phosphorylated gem-diol of formaldehyde. Synthetic methods, chemical properties and examples of practical applications are given.

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Section: General Chemical Properties Of Phosphorylated Formaldehydmentioning

confidence: 99%

Section: Phosphorylated Formaldehyde Halogenoaminals (Phosphorylatmentioning

confidence: 99%

Section: Phosphorylated Formaldehyde Halogenoaminals (Phosphorylatmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Chemistry of Phosphorylated Formaldehyde Derivatives. Part I

Morgalyuk

2014

Molecules

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“…In contrast, aminoalkylation of enamines proceeded with very high diastereoselectivity as only one diastereoisomer 57 was observed by NMR spectroscopy. Mannich bases 57 easily eliminate the amino group by simple stirring a solution of 57 in dichloromethane in the presence of silica gel to give substituted vinylphosphonates 58 (Scheme 5.26) [131].…”

Section: Syntheses Using Càn and Càc Bond-forming Reactionsmentioning

confidence: 99%

Chemistry of Aminophosphonic Acids and Phosphonopeptides

Kukhar

Romanenko

2009

Amino Acids, Peptides and Proteins in Organic Chemistry

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Aminophosphonic (and aminophosphinic) acids occupy a prominent position in the understanding of bioprocesses in living organisms and in the construction of new bioregulators -pharmaceuticals and agrochemicals. The so-called phosphorus analogs of the amino acids, aminophosphonic and aminophosphinic acids, are amino acid mimetics in which the carboxylic group is substituted by a phosphonic acid residue P(O)(OH) 2 or phosphinic acid group P(O)(OH)R. The replacement of the carboxylic group by a phosphonic or related moiety results in a number of important consequences: the central atom of a phosphonic acid function consists of an additional substituent that has a tetrahedral configuration in contrast to the planar carbonyl atom of carboxylic group. There are also significant differences in the acidity and steric bulk of these residues. The tetrahedral configuration of the pentavalent phosphorus atom mimics the transition state of the peptide bond cleavage reaction in some enzyme-substrate interactions that is used in the synthesis of new inhibitors. The hydrolytic stability of CÀP bonds is often used in order to prepare stable analogs of bioactive phosphates OÀP(O)(OH) 2 . In addition, aminophosphonic acids and their derivatives are important as metal-complexing agents, which have diagnostic and therapeutic applications, and as industrial chemicals in water treatment, metal extraction, or pollution control.Synthesis, and the chemical, physical, and biological properties of aminophosphonic acids and some directions for their practical application are presented in a number of reviews and book chapters. The most comprehensive account of the chemistry and biology of aminophosphonates and aminophosphinate which covers literature up to 2000 is presented in Kukhar and Hudson ([1] and references therein). Readers are referred to this reference for more detailed information concerning specific aspects of the chemistry and biological activity of aminophosphonic acid derivatives. The purpose of this chapter is to give an updated report on aminophosphonic acids as analogs of amino acids. Numerous heterocyclic compounds that contain both phosphonic and amino groups will not be covered in this report.

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Nutzung von elektronenarmen Iminiumintermediaten zur Synthese von wertvollen Aminen

et al. 2022

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Die Entwicklung von Reaktionen zur Umwandlung von Alkenen und Alkinen in wertvolle Bausteine ist nach wie vor eines der Hauptziele in der synthetischen Chemie. In dieser Arbeit berichten wir von der Nutzbarmachung von stark elektronenarmen, seltenen und kurzlebigen Iminiumionen zur Synthese von Aminen. Dies ermöglicht die milde Herstellung von Aminen mit z. B. trifluormethylierten Einheiten. Dieses umfassende Konzept wird durch die Aminierung von Chinin zu einem biologisch interessanten neuen Analogon verdeutlicht.

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An Efficient Synthesis of Novel α‐Aminophosphonates Based on a Mannich‐Type Reaction

Cited by 12 publications

References 59 publications

Chemistry of Phosphorylated Formaldehyde Derivatives. Part I

Chemistry of Phosphorylated Formaldehyde Derivatives. Part I

Chemistry of Aminophosphonic Acids and Phosphonopeptides

Nutzung von elektronenarmen Iminiumintermediaten zur Synthese von wertvollen Aminen

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