Uncatalyzed One‐Pot Diastereoselective Synthesis of α‐Amino Phosphonates Under Solvent‐Free Conditions

Tibhe, Gaurao D.; Lagunas‐Rivera, Selene; Vargas-Dı́az, Marı́a Elena; García-Barradas, Óscar; Ordóñez, Mario

doi:10.1002/ejoc.201001096

Cited by 29 publications

(16 citation statements)

References 55 publications

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“…A mixture of the different reactants, which contained an aliphatic or aromatic aldehyde, chiral amine [(S)-α-methylbenzylamine, (S)-1-(1-naphthyl)ethylamine or (S)-3,3-dimethyl-2-butylamine] and dimethyl phosphite, was heated at 80°C for 5-8 h (Scheme 1). [7] RESULTS AND DISCUSSION…”

Section: Synthetic Methodologymentioning

confidence: 99%

Study of the fragmentation pathway of α‐aminophosphonates by chemical ionization and fast atom bombardment mass spectrometry

Tibhe

Labastida-Galván

Ordóñez

2011

Rapid Comm Mass Spectrometry

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The diastereoisomers of α-aminophosphonates are key intermediates in the synthesis of enantiomerically pure α-aminophosphonic acids, which are analogs of α-amino acids. Although several methods have been reported for the diastereoselective synthesis of α-aminophosphonates, their mass spectrometry (MS) fragmentation patterns have not yet been fully investigated. The work described here involved a detailed study of the fragmentation of enriched α-aminophosphonate diastereoisomers by chemical ionization (CI-MS) and fast atom bombardment (FAB)-MS. The complete characterization of the different conventional MS fragmentation pathways is represented and this intriguing exercise required the use of tandem mass spectrometry (MS/MS) experiments and high-resolution accurate mass measurements. All α-aminophosphonates gave prominent pseudomolecular ions, protonated molecules [MH](+) , and their fragmentations mainly showed a loss of dimethyl phosphite to give the corresponding iminium ions as base peaks for α-aminophosphonates bearing methylbenzyl and 2,2-dimethylbutyl fragments. The loss of the chiral fragment from the iminium ions bearing the (S)-1-(1-naphthyl)ethyl group gave rise to a base peak due to aryl cations. The nature of all fragment ions were confirmed by high-resolution mass spectrometry (HRMS).

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Section: Synthetic Methodologymentioning

confidence: 99%

Study of the fragmentation pathway of α‐aminophosphonates by chemical ionization and fast atom bombardment mass spectrometry

Tibhe

Labastida-Galván

Ordóñez

2011

Rapid Comm Mass Spectrometry

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“…Generally, the high diastereoselective ratio can be explained on the basis of the most stable conformation of the Schiff bases, in which the C-H bond of the imine is eclipsed with the N-C-H fragment, as would be expected from the 1,3-allylic strain model [36,37], and the nucleophilic Simple pseudopeptides containing α-amino-C-phosphinate moieties replacing the scissile peptide bonds, rank among most potent inhibitors of metalloproteinases, where their tumorigenesis and invasion-related functions makes these enzymes molecular targets for the development of potential anticancer drugs [23]. The role of neutral aminopeptidase in the pathogenesis of hypertension provides an opportunity for regulating arterial blood pressure through its inhibition with this class of compounds [24].…”

Section: Stereoselective C-p Bond Formation (Addition Of Phosphorus Cmentioning

confidence: 99%

Stereoselective Synthesis of α-Amino-C-phosphinic Acids and Derivatives

et al. 2016

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α-Amino-C-phosphinic acids and derivatives are an important group of compounds of synthetic and medicinal interest and particular attention has been dedicated to their stereoselective synthesis in recent years. Among these, phosphinic pseudopeptides have acquired pharmacological importance in influencing physiologic and pathologic processes, primarily acting as inhibitors for proteolytic enzymes where molecular stereochemistry has proven to be critical. This review summarizes the latest developments in the asymmetric synthesis of acyclic and phosphacyclic α-amino-C-phosphinic acids and derivatives, following in the first case an order according to the strategy used, whereas for cyclic compounds the nitrogen embedding in the heterocyclic core is considered. In addition selected examples of pharmacological implications of title compounds are also disclosed.

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“…3,4 Many natural and synthetic α-aminophosphonates and their derivatives have greater prominence as anti-HIV, cancer, biotic, bacterial, tumor, and antiviral agents. [5][6][7][8][9][10] Furthermore, α-aminophosphonates are used in agricultural industry as fungicidal, herbicidal agents, and plant growth regulators. [11][12][13] Consequently, different methods have been developed for their synthesis.…”

Section: Introductionmentioning

confidence: 99%

“…Hz, P OCH 2 CH 3 ), 3.76-3.92 (2H, m, P OCH 2 CH 3 ), 3.96-4.14 (2H, m, P OCH 2 CH 3 ), 4.80 (1H, d, J = 25.0 Hz, P CH),5.04 (2H, s, OCH 2 O), 6.28 (1H s, NH), 6.65-7.58 (6H, m, Ar H) 31. P NMR (202.4 MHz, CDCl 3 ) δ: 22.18.…”

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confidence: 99%

Tween-20: An Efficient Catalyst for One-Pot Synthesis of α-Aminophosphonates in Aqueous Media

Sundar

Srinivasulu

Nayak

et al. 2012

Phosphorus, Sulfur, and Silicon and the Related Elements

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A green one-pot three-component synthesis has been developed for α-aminophosphonates by condensation of aldehydes, amines, and diethylphosphite by using nonionic surfactant Tween-20 as catalyst in aqueous media. The results showed that this synthetic route for α-aminophosphonates takes just 25-60 min for completion at 60 • C and affords 64%-91% yields depending on the nature of the amine substrates. The major advantages of this novel method are green reaction conditions with water as solvent, simple workup, less reaction times, and high to moderate yields.

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Uncatalyzed One‐Pot Diastereoselective Synthesis of α‐Amino Phosphonates Under Solvent‐Free Conditions

Abstract: Uncatalyzed one-pot, three-component reactions of aldehydes, chiral α-methylamines, and dimethyl phosphite under solvent-free conditions were used for the diastereoselective synthesis of α-amino phosphonates. The reactions proceeded

Cited by 29 publications

References 55 publications

Study of the fragmentation pathway of α‐aminophosphonates by chemical ionization and fast atom bombardment mass spectrometry

Study of the fragmentation pathway of α‐aminophosphonates by chemical ionization and fast atom bombardment mass spectrometry

Stereoselective Synthesis of α-Amino-C-phosphinic Acids and Derivatives

Tween-20: An Efficient Catalyst for One-Pot Synthesis of α-Aminophosphonates in Aqueous Media

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