36198-87-5Relevant articles and documents
Diphosphonylation of aromatic diazaheterocycles and theoretical rationalization of product yields
De Blieck, Ann,Catak, Saron,Debrouwer, Wouter,Drabowicz, Jozef,Hemelsoet, Karen,Verstraelen, Toon,Waroquier, Michel,Van Speybroeck, Veronique,Stevens, Christian V.
, p. 1058 - 1067 (2013)
Diphosphonylated diazaheterocyclic compounds were synthesized in a one-step reaction by using dimethyl trimethylsilyl phosphite (DMPTMS) under acidic conditions. The reaction of DMPTMS with 1,5-naphthyridine yielded the corresponding diphosphonylated product through a tandem 1,4-1,2 addition under microwave conditions. This tandem 1,4-1,2 addition was also evaluated for other substrates, namely, 1,10-phenanthroline, 1,7-phenanthroline and 4,7-phenanthroline. Reactions under reflux and microwave conditions were compared. 1,5-Naphthyridine and the phenanthroline derived substrates are less reactive than previously investigated quinolines. The experimental trends in reactivity were rationalized by means of theoretical calculations. The intrinsic properties, such as aromaticity and proton affinities, showed distinct differences for the various substrates. Furthermore, the calculated free energies of activation for the rate-determining step of the tandem addition reaction enabled us to rationalize the differences in product yields. Both the theoretical and the experimental results show the substantial influence of the position of the nitrogen atoms in the (poly)aromatic compounds on the reaction outcome. Diphosphonylated diazaheterocyclic compounds are synthesized in a one-step reaction from naphthyridines and phenanthrolines by using dimethyl trimethylsilyl phosphite (DMPTMS). The substrate has a profound influence on the product yields for the tandem 1,4-1,2-addition. The product yields are theoretically rationalized by evaluating proton affinities, aromaticities and free energies of activation. Copyright
Tandem Addition of Phosphite Nucleophiles Across Unsaturated Nitrogen-Containing Systems: Mechanistic Insights on Regioselectivity
Debrouwer, Wouter,Hertsen, Dietmar,Heugebaert, Thomas S. A.,Boydas, Esma Birsen,Van Speybroeck, Veronique,Catak, Saron,Stevens, Christian V.
, p. 188 - 201 (2017/04/26)
The addition of phosphite nucleophiles across linear unsaturated imines is a powerful and atom-economical methodology for the synthesis of aminophosphonates. These products are of interest from both a biological and a synthetic point of view: they act as amino acid transition state analogs and Horner-Wadsworth-Emmons reagents, respectively. In this work the reaction between dialkyl trimethylsilyl phosphites and α,β,γ,δ-diunsaturated imines was evaluated as a continuation of our previous efforts in the field. As such, the first conjugate 1,6-addition of a phosphite nucleophile across a linear unsaturated N-containing system is reported herein. Theoretical calculations were performed to rationalize the observed regioselectivites and to shed light on the proposed mechanism.
One-pot tandem 1,4-1,2-addition of phosphites to quinolines
De Blieck, Ann,Masschelein, Kurt G. R.,Dhaene, Frederic,Rozycka-Sokolowska, Ewa,Marciniak, Bernard,Drabowicz, Jozef,Stevens, Christian V.
supporting information; experimental part, p. 258 - 260 (2010/04/30)
Trialkyl and silylated dialkyl phosphites were evaluated as phosphorus nucleophiles for the addition to quinolines in a strong acidic medium allowing consecutive 1,4- and 1,2-addition breaking up the aromatic stabilisation, thereby leading to 2,4-diphosphono-1,2,3,4-tetrahydroquinolines in one single reaction step in moderate to good yields (2-84%).
5-Phosphonomethylquinoxalinediones as competitive NMDA receptor antagonists with a preference for the human 1A/2A, rather than 1A/2B receptor composition
Auberson, Yves P,Allgeier, Hans,Bischoff, Serge,Lingenhoehl, Kurt,Moretti, Robert,Schmutz, Markus
, p. 1099 - 1102 (2007/10/03)
NMDA antagonists derived from 5-phosphonomethyl-1,4-dihydroquinoxaline-2,3-dione (3a) are potent anticonvulsant agents, and display strong protective effects in the electroshock-induced convulsion assay in mice. Their preference for the human NMDAR 1A/2A over 1A/2B subunit composition was optimized, leading to (1RS,1′S)-PEAQX (9r), which shows a >100-fold selectivity.
Application of bromotrimethylsilane and trialkyl phosphites for convenient and effective synthesis of aminophosphonic acids and corresponding monoalkyl and dialkyl esters
Boduszek
, p. 663 - 672 (2007/10/03)
Application of bromotrimethylsilane (Br-TMS) in a mixture with trialkyl phosphite for synthesis of various aminophosphonic acids and esters was investigated. It was found, that appropriate mixtures of Br-TMS and trimethyl phosphite or triethyl phosphite were effective reagents for phosphorylation of various aldimines, obtained from aromatic and heteroaromatic aldehydes. Products of these reactions were corresponding aminophosphonic acids, or corresponding dialkyl or monoalkyl esters, respectively.
Synthesis and plant growth regulating activity of new triazolo- and pyrazolopyrimidine derivatives of aminomethyl-, aminoalkyloxymethyl dimethylphosphine oxides and (aminomethane)phosphonic acid esters
Stanoeva, Elena,Varbanov, Sabi,Alexieva, Vera,Sergiev, Iskren,Vasileva, Vesselina,Rashkova, Marieta,Georgieva, Angelina
, p. 117 - 133 (2007/10/03)
New triazolo[4,5-d]pyrimidine and pyrazolo[3,4-d]pyrimidine derivatives of aminomethyl- and aminomethyloxymethyl dimethylphosphine oxides 8-14 as well as of esters of (aminomethane) phosphonic acid 18-20 were synthesized. The structure of the compounds prepared was confirmed by means of elemental analysis, IR, 1H- and 31P{1H}-NMR spectroscopy. Tertiary phosphine oxides 8, 9 and 12 as well as phosphonate 20 showed herbicidal and plant growth regulating activity.
A FACILE SYNTHESIS OF TRIALKYLSILYLPHOSPHITES AND PHOSPHATES
Li, Zhonghua,Zhu, Chuanfang,Zhao, Yongzhen
, p. 229 - 232 (2007/10/02)
Trialkylsilylphosphites (1a-1d) and trialkylsilylphosphates (2a-2d) were synthesized in good yield by a facile method.The method could be easily used to prepare P-O-Si bond and P-Si bond compounds from dialkylphosphites and trialkylchlorosilanes.Key words: Phosphates; trialkylsilylphosphites; trialkylchlorosilanes.
Addition of Dialkyl Phosphites and Dialkyl Trimethylsilyl Phosphites to 2-(Benzyloxy)propanal - Preparation of all Four Stereoisomeric (1,2-Dihydroxy-2H1>propyl)phosphonic Acids from Chiral Lactates
Hammerschmidt, Friedrich
, p. 469 - 475 (2007/10/02)
Dimethyl trimethylsilyl phosphite, diisopropyl trimethylsilyl phosphite, dimethyl phosphite, and diisopropyl phosphite were added to 2-(benzyloxy)propanals 4 and 6 at different temperatures in THF and CH2Cl2.The ratio of diastereomers formed was highest for diisopropyl trimethylsilyl phosphite (erythro/threo 3:1) and dropped to about 1:1 for diisopropy phosphite.Starting from chiral lactates all four stereoisomeric diisopropyl (2-benzyloxy-1-hydroxy-2H1>phosphonates were prepared and deprotected.The (1,2-dihydroxy-2H1>propyl)phosphonic acids formed were purified as cyclohexylammonium salts.The relative configuration of phosph onic acid of (-)-11 was determined by comparison with the salt (1R,2R)-12 derived from fosfomycin.
Silyl Phosphites. Part 20. A Facile Synthesis pf Phosphoenolpyruvate and Its Analogue Utilizing in siti Generated Trimethylsilyl Bromide
Sekine, Mitsuo,Futatsugi, Tetsuaki,Yamada, Kohji,Hata, Tsujiaki
, p. 2509 - 2514 (2007/10/02)
Phosphoenolpyruvate (PEP) has been synthesized from pyruvic acid and dimethyl trimethylsilyl phosphite in high yield by a new route which involves, successively, trimethylsilylation, bromination, and a Perkow reaction.A PEP analogue of 1-(dihydroxyphosphinyl)vinyl phosphate (1) has also been prepared.
