Synthesis of Enantiomerically Pure (1S,2S)-1-Aminocyclopropanephosphonic Acids from (2S)-Methylcyclopropanone Acetal

Fadel, Antoine; Tesson, Nicolas

doi:10.1002/1099-0690(200006)2000:11<2153::aid-ejoc2153>3.0.co;2-x

Cited by 47 publications

(18 citation statements)

References 37 publications

(7 reference statements)

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“…The estimation of the optical purity of the (1-aminocyclopropyl) phosphonates substituted in the ring was performed by 31 Р NMR method on the corresponding diastereomeric amides obtained by treating the aminophosphonate with the Mosher's acid chloride [18,20,25].…”

Section: Syntheses Based On (Benzylideneaminomethyl) Phosphonic Acid mentioning

confidence: 99%

“…At the phosphorylation with trimethylphosphite (in methanol) the selectivity of the process somewhat decreased: isomeric dimethyl (1S,2S,1'S) and (1R,2S,1'S)-[2-methyl-1-(1-phenylethylamino)cyclopropyl]phosphonates formed in the ratio 80:20 (overall yield 67%) [25].…”

Section: Addition Of Phosphites To Cyclopropylideneiminium Cationsmentioning

confidence: 99%

“…1-Phenylethyl protection group on the nitrogen is easily removed by hydrogen on the Pearlman's catalyst at the room temperature [25,26]; therewith the diethoxy and dimethoxyphosphoryl group remained intact. For the simultaneous removal of the N-formyl group the hydrogenation is performed in 2 N HCl [29] (Scheme 8).…”

Section: Addition Of Phosphites To Cyclopropylideneiminium Cationsmentioning

confidence: 99%

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Synthesis methods of (1-aminocyclopropyl)phosphonic acids

2011

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Section: Syntheses Based On (Benzylideneaminomethyl) Phosphonic Acid mentioning

confidence: 99%

Section: Addition Of Phosphites To Cyclopropylideneiminium Cationsmentioning

confidence: 99%

Section: Addition Of Phosphites To Cyclopropylideneiminium Cationsmentioning

confidence: 99%

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Synthesis methods of (1-aminocyclopropyl)phosphonic acids

2011

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“…Thus many cyclic a-aminophosphonic acids bearing the exocyclic amino group were prepared mostly in racemic series [10][11][12][13][14]. However, among a-aminophosphonates those containing nitrogen as a ring heteroatom are scarce.…”

Section: Introductionmentioning

confidence: 99%

Facile synthesis of cyclic α-perfluoroalkyl-α-aminophosphonates

Odinets

Аrtyushin

Shevchenko

et al. 2009

Journal of Fluorine Chemistry

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“…28 In the 31 P NMR spectrum all synthesized a-aminophosphonates have signals at d = 22.00-31.00 ppm which are typical for compounds of this class. 24 1 H NMR spectra of a-aminophosphonates can be quite complicated due either possible existence of diastereomers or diastereotopy of some groups or both. Indeed, in some cases [ Table 1: 3-methylcyclohexanone (1), 4-tertbutylcyclohexanone (4), camphor (11), norbornanone (12)] one has to take into account the possible formation of mixtures of cis-and trans-isomers.…”

mentioning

confidence: 99%

A Novel Catalytic Three-Component Synthesis (Kabachnick-Fields Reaction) of α-Aminophosphonates from Ketones

Matveeva¹,

Podrugina²,

Tishkovskaya³

et al. 2003

Synlett

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A novel and highly convenient catalytic variant of the synthesis of a-aminophosphonates on basis of the KabachnikFields reaction [three-component reaction of ketones, diethylphosphite and either benzylamine (series a) of ammonium carbonate (series b)] in the presence of tetra-tert-butylphthalocyanines has been developed. This method affords a-aminophosphonates in acceptable yields for various ketones, including cyclic, sterically hindered and cage ketones. The unsubstituted a-aminophosphonic acids were also obtained from the corresponding esters of series b.a-Aminophosphonic acids may be considered as phosphorous analogues of a-amino acids ('bioisosterism'), 1 and have received considerable attention owing to their pronounced biological activities. These entities have been shown to serve as inhibitors of GABA-receptors, inhibitors of various proteolytic enzymes, inhibitors of dialkylglycine decarboxylase, peptide mimetics, antibiotics, and pharmacological agent, including antitumor, antihypertensive and antibacterial agents. [2][3][4][5][6][7][8][9][10][11][12][13][14][15] Various synthetic methods for a-aminophosphonic acids and a-aminophosphonates have therefore been reported. 5,8,9 However, the classical approach to their synthesis is the Kabachnik-Fields reaction, 10-15 which is a one-pot, three-component operation with carbonyl compound, amine and dialkyl phosphite. This approach is especially satisfactory for reactions with aldehydes, and this protocol was even used for parallel synthesis. 16 In contrast, only a scarce example of the reaction of rather simple ketones (mainly, acetone, acetophenone and cyclohexanone) has been documented. 2,4,7,9 The mechanism of this reaction is still not clearly understood, 12-14 but one of many possible pathways includes nucleophilic addition of phosphites to the transient imines. In fact, reaction of phosphites with imines is really promoted by alkali metal alkoxide or Lewis acids. 17,18 In principle, the Kabachnik-Fields reaction (a three-component process) can also be catalyzed by an acid or base. Indeed, there are also a few examples of catalytic variants of this reaction, and lanthanide triflate/magnesium sulfate, 19 scandium(tris-dodecyl sulfate), 20 lanthanide triflates/ionic liquids 21 and indium(III) chloride 7 were used as the catalysts. The first three examples were satisfactory mainly for aromatic aldehydes; the last one included aliphatic aldehydes and only few ketones. Thus, an efficient procedure for synthesis of a-aminophosphonic acids and aaminophosphonates from ketones, especially hindered ones, is needed.In this report, we describe a novel and efficient catalytic method for the synthesis of a-aminophosphonates and aaminophosphonic acids with the involvement of various ketones. The reactions were performed with diethylphosphite and amines in presence of tetra-tert-butyl-substituted phthalocyanines Pht-1-Pht-3 22 as catalysts. Figure 1 Pht-1 M = AlCl; Pht-2 M = Co(II); Pht-3 M = Ni(II)First, the reaction of 3-methylcyclohexanone, 1, with benzylamine and di...

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Synthesis of Enantiomerically Pure (1S,2S)-1-Aminocyclopropanephosphonic Acids from (2S)-Methylcyclopropanone Acetal

Cited by 47 publications

References 37 publications

Synthesis methods of (1-aminocyclopropyl)phosphonic acids

Synthesis methods of (1-aminocyclopropyl)phosphonic acids

Facile synthesis of cyclic α-perfluoroalkyl-α-aminophosphonates

A Novel Catalytic Three-Component Synthesis (Kabachnick-Fields Reaction) of α-Aminophosphonates from Ketones

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