ChemInform Abstract: Application of Bis(trimethylsilyl) Phosphonite in the Efficient Preparation of New Heterocyclic α-Aminomethyl-H-phosphinic Acids (original) (raw)
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Synthesis, 2011
A simple, reproducible, and efficient preparation of new heterocyclic a-aminomethyl-H-phosphinic acids is reported. The synthetic protocol is based on the application of bis(trimethylsilyl) phosphonite, as an efficient phosphorous nucleophile, in the reaction with the corresponding heterocyclic imines. Subsequent methanolysis of the addition intermediates leads to the expected heterocyclic a-aminomethyl-H-phosphinic acids in fair to good yields. Additionally, acidic hydrolysis of benzhydrylamino derivatives allows the efficient preparation of free a-aminomethyl-Hphosphinic acids in good yields and high purity after simple crystallization.
Synthesis
A simple, reproducible, and efficient preparation of new heterocyclic a-aminomethyl-H-phosphinic acids is reported. The synthetic protocol is based on the application of bis(trimethylsilyl) phosphonite, as an efficient phosphorous nucleophile, in the reac-tion with the corresponding heterocyclic imines. Subsequent meth-anolysis of the addition intermediates leads to the expected heterocyclic a-aminomethyl-H-phosphinic acids in fair to good yields. Additionally, acidic hydrolysis of benzhydrylamino deriva-tives allows the efficient preparation of free a-aminomethyl-H-phosphinic acids in good yields and high purity after simple crystal-lization. a-Aminoalkyl-H-phosphinic acids, as isosters of the natu-ral a-aminoalkylcarboxylic acids, and short peptides in-corporating this unit (i.e., phosphinic acid peptides) represent a very convenient mimic of a substrate in the transition state of hydrolytic enzymes and, therefore, they are considered as excellent enzyme inhibitors. 1 The effi-cie...
Organocatalytic synthesis of α-hydroxy and α-aminophosphonates
Tetrahedron Letters, 2008
a-Hydroxy phosphonate Solvent-free a-Aminophosphonates a b s t r a c t A new and highly flexible procedure is described for the synthesis of a-aminoand a-hydroxy phosphonates. In the presence of a catalytic amount of oxalic acid (10 mol %), trimethyl phosphite reacts with aldehydes or imines (generated in situ from an aldehyde and an amine) to yield the corresponding coupled products in good yield.
A General Protocol for the Synthesis of H-α-Hydroxyphosphinates
Synthesis, 2018
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A convenient synthetic route towards H-bisphosphinates
Organic and Biomolecular Chemistry, 2018
A practical general route to 1-hydroxymethylene-1,1-bis(H-phosphinates) has been developed. Diverse alkyl or (hetero)aryl bisphosphinates were rapidly obtained in satisfying to excellent yields from corresponding acid chlorides and in situ generated bis(trimethylsilyl)phosphonite. This work is complementary to previous approaches. A generalisable procedure was optimised allowing the description of numerous compounds. To check the literature data, a pka value study was also performed.
Molecules, 2020
α-Aminophosphonic acids are phosphorus analogues of α-amino acids. Compounds of this type find numerous applications in medicine and crop protection due to their unique biological activities. A crucial factor in these activities is the configuration of the stereoisomers. Only a few methods of stereoselective transformation of α-amino acids into their phosphorus analogues are known so far and all of them are based on asymmetric induction, thus involving the use of a chiral substrate. In contrast, we have focused our efforts on the development of an effective method for this type of transformation using a racemic mixture of starting N-protected α-amino acids and a chiral catalyst. Herein, a simple and efficient stereoselective organocatalytic α-amidoalkylation of dimethyl phosphite by 1-(N-acylamino)alkyltriphenylphosphonium salts to enantiomerically enriched α-aminophosphonates is reported. Using 5 mol% of chiral quinine- or hydroquinine-derived quaternary ammonium salts provides fin...
Tetrahedron Letters, 2005
New a-aminophosphonates of the type (OCH 2 CMe 2 CH 2 O)P(O)CH(NHCO 2 R)(R 0 ) [6a-i, 7a-e, and 8a-c] have been synthesized in high yields by a three-component reaction using (OCH 2 CMe 2 CH 2 O)PCl (3), benzamide (or urethane or benzyl carbamate), and an aldehyde without using any catalyst under solvent-free conditions. This route can be readily adapted for bisaminophosphonates as well as optically active binaphthoxy a-aminophosphonates; it also tolerates the phenolic -OH group as shown by the synthesis of hydroxy functionalized aminophosphonates. Partial hydrolysis of compounds 7a-d leads to products in which the phosphorinane ring is cleaved first. Compounds (OCH 2 CMe 2 CH 2 O)P(O)CH[NHC(O)Ph](9-anthryl) (6f) and optically pure (R,S)-(À)-(C 20 H 12 O 2 )P(O)CH(NHCO 2 Et)(Ph) (14a) were characterized by X-ray crystallography.
Journal of Molecular Structure
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