- A Highly Convenient Route to Optically Pure α-Aminophosphonic Acids
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Pure diastereomers, obtained simply and directly by reaction of hypophosphorous acid salts of (R)(+) or (S)(-) - N-α-methylbenzylamine with aldehydes, can be simultaneously deprotected and oxidised in one step to provide a highly convenient synthesis of α-aminophosphonic acids in high optical purity.
- Hamilton, Robert,Walker, Brian,Walker, Brian J.
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- Asymmetric synthesis of aminophosphonic acids
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A new synthesis of chiral α- and β-aminophosphonic acids is described which involves a highly diastereoselective addition of phosphite and phosphonate anions to enantiopure sulfinimines.
- Miko?ajczyk, Marian,?yzwa, Piotr,Drabowicz, Józef
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- Highly diastereoselective addition of chiral H-phosphonate to tert-butylsulfinyl aldimines: a convenient approach to (R)-α-aminophosphonic acids
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Abstract A highly diastereoselective nucleophilic addition of chiral H-phosphonate, derived from a readily available TADDOL auxiliary, to (S)-N-tert-butylsulfinyl aldimines is reported. The reaction proceeds at room temperature in the presence of potassium carbonate and yields the corresponding aliphatic, aromatic and heteroaromatic α-aminophosphonates with dr >95:5. Subsequent simultaneous removal of both chiral auxiliaries leads to the desired α-aminophosphonic acids in very good yields with an (R)-configuration at the stereogenic α carbon.
- Olszewski, Tomasz K.,Majewski, Mateusz
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p. 846 - 852
(2015/08/18)
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- Double asymmetric induction in the synthesis of enantiomeric α-aminophosphonic acids mediated by sulfinimines
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A double asymmetric induction in the synthesis of α-aminophosphonic acids is described. It involves the nucleophilic addition of anions of enantiomeric dimenthyl phosphites to both (+)-(S)- and (-)-(R)-enantiomers of N-(p-tolylsulfinyl)benzaldimine and subsequent acidic hydrolysis of the adducts formed. The match and mismatch effects were observed.
- Lyzwa, Piotr
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- Biocatalyzed kinetic resolution of racemic mixtures of chiral α-aminophosphonic acids
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Several fungal species namely: Aspergillus niger, Aspergillus parasiticus, Penicillium funiculosum, Trigonopsis variabilis and two different strains of Fusarium oxysporum were tested toward racemic mixtures of following phosphonic acids: 1-amino-2-methylp
- Kozyra, Kinga,Brzezinska-Rodak, Malgorzata,Klimek-Ochab, Magdalena,Zymanczyk-Duda, Ewa
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- Highly enantioselective conjugate additions of phosphites to α β-unsaturated N-acylpyrroles and imines: A practical approach to enantiomerically enriched amino phosphonates3
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The first highly enantioselective phosphonylation of αβ- unsaturated N-acylpyrroles has been developed. Excellent yields (91-99%) and enantioselectivities (up to >99% enantiomeric excess (ee)) were observed for a broad spectrum of both phosphites and N-ac
- Zhao, Depeng,Wang, Yuan,Mao, Lijuan,Wang, Rui
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supporting information; experimental part
p. 10983 - 10987
(2010/04/30)
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- 1-(a-Aminobenzyl)-2-naphthol: A new chiral auxiliary for the synthesis of enantiopure a-aminophosphonic acids
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A new diastereoselective synthesis of a-aminophosphonates has been developed, based on the reaction, in the presence of trifluoroacetic acid, of trialkyl phosphites with chiral imines derived from (R)- or (S)-l-(ot- aminobenzyl)-2-naphthol. The reaction p
- Metlushka, Kirill E.,Kashemirov, Boris A.,Zheltukhin, Viktor F.,Sadkova, Dilyara N.,Buechner, Bernd,Hess, Christian,Kataeva, Olga N.,McKenna, Charles E.,Alfonsov, Vladimir A.
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supporting information; experimental part
p. 6718 - 6722
(2010/02/28)
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- Catalytic enantioselective pudovik reaction of aldehydes and aldimines with tethered bis(8-quinolinato) (TBOx) aluminum complex
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New chiral tethered bis(8-quinolinolato) (TBOx) aluminum(III) complexes effectively catalyze the addition of phosphites to aldehydes and aldimines to give enantioenriched α-hydroxy and α-amino phosphonates in high yields and enantioselectivities with unpr
- Abell, Joshua P.,Yamamoto, Hisashi
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body text
p. 10521 - 10523
(2009/02/04)
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- A new and convenient asymmetric synthesis of α-amino- and α-alkyl-α-aminophosphonic acids using N-tert-butylsulfinyl imines as chiral auxiliaries
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Nucleophilic addition of dialkyl phosphites to N-tert-butylsulfinyl aldimines or ketimines occurs successfully at room temperature with potassium carbonate as base to afford α-amino- and α-alkyl-α-amino-N- (tert-butylsulfinyl)phosphonates in good to excel
- Chen, Qianyi,Yuan, Chengye
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p. 3779 - 3786
(2008/09/18)
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- Straightforward synthesis of depsiphosphonopeptides via Mannich-type multicomponent condensation
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A straightforward method for the synthesis of depsiphosphonopeptides via a Mannich-type multicomponent condensation of simple starting materials, such as benzyl carbamate, aldehydes, and 1-carbethoxyalkyl phosphorodichloridites, was developed. Compared to
- Xu, Jiaxi,Gao, Yuanhe
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p. 783 - 788
(2007/10/03)
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- Thiourea-Catalyzed Enantioselective Hydrophosphonylation of Imines: Practical Access to Enantiomerically Enriched α-Amino Phosphonic Acids
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Chiral thiourea 1b catalyzes the highly enantioselective hydrophosphonylation of a wide range of N-benzyl imines. The hydrophosphonylation products are readily deprotected by hydrogenolysis, providing access to free α-amino phosphonic acids in highly enantioenriched form. Copyright
- Joly, Guy D.,Jacobsen, Eric N.
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p. 4102 - 4103
(2007/10/03)
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- Stereoselective Addition of Dimethyl Thiophosphite to Imines
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Dimethyl thiophosphite (DMTP) was synthesized from dimethyl phosphite, and the diastereoselective addition of DMTP to benzaldimines bearing chiral auxiliary groups was examined. Yields of the product α -aminophosphonothionates ranged from 17% to 75% after chromatography. The addition of DMTP to the benzaldimine derived from (S)-phenylglycinol afforded the highest diastereoselectivity (83:17), whereas addition of DMTP to the benzaldimine derived from threonine methyl ester and alanine methyl ester were far less diastereoselective, affording 38:62 and 61:39 ratios, respectively. Addition of DMTP to the benzaldimine derived from (R)-α-methylbenzylamine (78:22) and (S)-serine methyl ester (73:27) were intermediate in selectivity. DMTP addition to the imines formed between serine methyl ester and acetaldehyde and isobutyraldehyde gave 55:45 and 70:30 ratios, respectively, with the diastereoselectivity corresponding roughly to the size of the α-alkyl group. The stereochemistry of the newly formed α-stereocenters resulting from the addition of DMTP to (S)- and (R)-phenylglycinol benzaldimines was confirmed by conversion of the product α-aminophosphonothionates to the known enantiomers of phosphonophenylglycine.
- Tongcharoensirikul, Pakamas,Suarez, Alirica I.,Voelker, Troy,Thompson, Charles M.
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p. 2322 - 2326
(2007/10/03)
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- A new efficient procedure for asymmetric synthesis of α-aminophosphonic acids via addition of lithiated bis(diethylamino)phosphine borane complex to enantiopure sulfinimines
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The addition of lithiated bis(diethylamino)phosphine borane complex to enantiopure p-toluenesulfinimines is highly diastereoselective, affording the corresponding addition products with high efficiency (yields from 72 to 100%). The addition products were readily converted into α-amino-α-arylmethylphosphonic acids with high enantiomeric purities (from 72 to >98%).
- Mikolajczyk, Marian,Lyzwa, Piotr,Drabowicz, Jozef
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p. 2571 - 2576
(2007/10/03)
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- Asymmetric synthesis of quaternary alpha-amino phosphonates using sulfinimines.
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The addition of lithium diethylphosphonate to enantiopure ketosulfinimines is highly diastereoselective (>95%), affording the first examples of quaternary alpha-alkyl alpha-amino (arylmethyl)phosphonates.
- Davis,Lee,Yan,Titus
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p. 1757 - 1760
(2007/10/03)
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- Synthesis of α-amino phosphonates under diastereocontrol by imidazolidin-2-one auxiliaries
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Ephedrine derived (4R,5S)-imidazolidin-2-one auxiliaries demonstrate phenomenal diastereocontrol in the addition of phosphite to chiral imine derivatives.
- Roos, Gregory H. P.,Balasubramaniam, Sundari
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p. 3877 - 3884
(2007/10/03)
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- Asymmetric addition of dialkyl phosphite and diamido phosphite anions to chiral, enantiopure sulfinimines: A new, convenient route to enantiomeric α-aminophosphonic acids
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Lithium or sodium dialkyl phosphites and diamido phosphites 3 undergo addition to (+)-(S)-benzylidene-p-toluenesulfinamide 2 affording N-sulfinyl-α-aminophosphonates 4 in a diastereoisomeric ratio from 63:37 to 94:6. The major diastereoisomers formed in addition of lithium dimethyl phosphite 3a and lithium bis-diethylamido phosphite 3e to (+)-(S)-2 were separated and converted into enantiopure (+)-(R)- and (-)-(S)-α-aminobenzyl phosphonic acids 5, respectively.
- Mikolajczyk, Marian,Llyzwa, Piotr,Drabowicz, Jozef
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p. 3991 - 3994
(2007/10/03)
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- Electrophilic amination and azidation of chiral α-alkyl phosphonamides: Asymmetric syntheses of α-amino α-alkyl phosphonic acids
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Stereoselective electrophilic aminations of chiral non racemic α-alkyl phosphonamides, derived from N,N'-dimethyl (R,R)-1,2-diaminocyclohexane, proceed with moderate to excellent enantioselectivities. The products are hydrolyzed and reduced to the corresponding α-alkyl α-amino phosphonic acids. The sense of asymmetric induction was confirmed by X-ray crystal structure analysis.
- Hanessian,Bennani
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p. 1272 - 1274
(2007/10/02)
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- STUDIES ON ORGANOPHOSPHORUS COMPOUNDS 78. NEW ASPECTS ON THE INDUCED ASYMMETRIC ADDITION OF DIALKYL PHOSPHITE TO ALDIMINES-AN EFFECTIVE SYNTHESIS OF CHIRAL 1-ARYLPHOSPHONOGLYCINE DERIVATIVES
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Addition of dialkyl phosphites to Schiff bases derived from (R)-2-methoxy-1-phenylethylamine or (R)-phenylglycine methyl ester afforded (1R,1'R)-1-arylphosphonoglycine derivatives with moderate to high diastereoselectivity.The influence of catalysts and s
- Yuan, Chengye,Li, Shusen,Wang, Guoquan,Ma, Yilin
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- Preparation of optically active 1-aminoalkylphosphonic acids by stereoselective enzymatic hydrolysis of racemic N-acylated 1-aminoalkylphosphonic acids
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N-Phenylacetylated derivatives of 1-aminoalkylphosphonic acids were synthesized and high enantioselectivity of their hydrolysis by penicillin acylase (EC 3.5.1.11) was demonstrated. Stereoselective enzymatic hydrolysis of racemic 1-(N-phenylacetylamino) alkylphosphonic acids was used for preparation of enantiomeric 1-aminoalkylphosphonic acids. The kinetic regularities of penicillin acylase catalyzed hydrolysis were established and the biocatalytic process was optimized to increase the optical purity and the yield of the optically active product.
- Solodenko,Kasheva,Kukhar,Kozlova,Mironenko,Svedas,Belozersky
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p. 3989 - 3998
(2007/10/02)
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- 133. Nucleophilic Additions to N-Glycosylnitrones. Part IV. Asymmetric Synthesis of N-Hydroxy-α-aminophosphonic and α-Aminophosphonic Acids
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The addition of phosphite anions and of tris(trimethylsilyl)phosphite (P(OSiMe3)3) to N-glycosyl-C-aryl-nitrones was examined.While these nitrones proved inert towards the phosphite anions, they reacted with P(OSiMe3)3 under catalysis by Lewis acids.Thus,
- Huber, Rolf,Vasella, Andrea
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p. 1461 - 1476
(2007/10/02)
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- A NON-SYMMETRICAL DIESTER OF 1-AMINO-1-PHENYLMETHANEPHOSPHONIC ACID. PART I. SYNTHESIS AND SEPARATION OF DIASTEREOISOMERS WITH A CHIRAL PHOSPHORUS ATOM
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Synthesis and separation of diastereoisomers of (R)-N-phthalyl-1-amino-1-phenylmethanephosphonic acid ethyl-2,2,2-trichloroethyl diester were described.These derivatives were converted to hydrochlorides and then to N-carbobenzoxy non-symmetrical diesters.
- Szewczyk, Jerzy,Hoffmann, Maria
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p. 325 - 330
(2007/10/02)
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- Optically active 1-aminoalkanephosphonic acids. Dibenzoyl-L-tartaric anhydride as an effective agent for the resolution of racemic diphenyl 1-aminoalkanephosphonates
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Optically active phosphonic analogues of alanine, valine, leucine, phenylalanine, and phenylglycine were obtained by resolution of diphenyl 1-aminoalkenephosphonates with dibenzoyl-L-tartaric acid anhydride.
- Kafarski, Pawel,Lejczak, Barbara,Szewczyk, Jerzy
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p. 2425 - 2430
(2007/10/02)
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