Dialkyl Trimethylsilyl Phosphites Research Articles

Improved facile synthesis of α-amino phosphonates by the reaction of α-amido sulfones with dialkyl trimethyl silyl phosphites catalyzed by Fe(III) chloride

ABSTRACTAn improved efficient synthesis of α-amino phosphonates has been discovered by the reaction of N-benzyloxycarbonylamino sulfones with dialkyl trimethyl silyl phosphites in the presence of FeCl3 as a catalyst. The products were formed in high yields (86–94%) within 2–4 h. The catalyst is inexpensive, easily available, and highly active. The unreacted dialkyl trimetyl silyl phosphites can easily be removed from the products due to their low boiling points. The sulfones can conveniently be prepared and are generally stable.

Tandem Addition of Phosphite Nucleophiles Across Unsaturated Nitrogen-Containing Systems: Mechanistic Insights on Regioselectivity

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.

Iodine-Catalyzed Efficient Hydrophosphonylation of N-Tosyl Aldimines

Treatment of N-tosyl aldimines with dialkyl trimethylsilyl phosphites at 0 degrees C in the presence of iodine as a catalyst afforded the corresponding sulfonamide phosphonates in excellent yields within 1.5 to 2.5 h.

Double Nucleophilic 1,2-Addition of Silylated Dialkyl Phosphites to 4-Phosphono-1-aza-1,3-dienes: Synthesis of γ-Phosphono-α-aminobisphosphonates

gamma-Phosphono-alpha-aminobisphosphonates were synthesized from a new class of 4-phosphono-1-aza-1,3-dienes by the addition of dialkyl trimethylsilyl phosphites to these azadienes in the presence of acid. Depending on the steric demand of the group on nitrogen, double 1,2-addition or tandem 1,4-1,2-addition occurred.

Nucleoside 5′- C-phosphonates: reactivity of the α-hydroxyphosphonate moiety

We found that various dialkyl phosphites, dialkyl trimethylsilyl phosphites, and tris-trimethylsilyl phosphite reacted smoothly with nucleoside 5′-aldehydes to afford epimeric nucleoside 5′- C-phosphonates in high yields. A number of these compounds in both the 2′-deoxyribo and ribo series were prepared. In the case of 2′-deoxythymidine-5′-aldehyde, a thorough study was made on the influence of the 3′-hydroxyl protecting group, type of phosphite, base, and solvent, on the yield and epimeric ratio of the resulting 5′-hydroxyphosphonates. Partial stereoselectivity in favour of either R or S epimers was observed. An attempt to transform the α-hydroxyl of the phosphonate moiety into a halo or azido moiety was not successful. Only intramolecular substitution reaction of the mesyloxy group for an alkoxy residue of the 2-hydroxyethyl ester took place in a low yield.

Electrochemically induced phosphorylation of alkenes

The processes of electrochemical phosphorylation of alkenes were investigated. It was found that anodically generated radical-cations of trialkyl phosphites, dialkyl trimethylsilyl phosphites, mono- and diamidophosphites were added to olefin molecules to give unsaturated alkenephosphonates. The anodic oxidation of tetraalkyl pyrophosphites proceeds with disintegration of initial radical-cations and leads to mixture alkane- and alkenephosphonates. Greater amounts of alkanephosphonates were formed during anodic oxidation of sodium (or lithium) dialkyl phosphites in the presence of alkenes.

An expedient synthesis of symmetrical tetra-alkyl monothiopyrophosphates

The reaction of readily available dialkyltrimethylsilyl phosphites (RO) 2POSiMe 3 5 with sulfur dichloride leads to tetra-alkyl sym-monothio-pyrophosphates (RO) 2P(O)SP(O)(OR) 2 1 in high yield. The method is suitable for the synthesis of tetra t-butyl thiopyrophosphate 1d.

ChemInform Abstract: Addition of Dialkyl Phosphites and Dialkyl Trimethylsilyl Phosphites to 2‐(Benzyloxy)propanal ‐ Preparation of all Four Stereoisomeric (1,2‐ Dihydroxy‐(1‐2H1)propyl)phosphonic Acids from Chiral Lactates.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Addition von Dialkylphosphiten und Dialkyl(trimethylsilyl)phosphiten an 2‐(Benzyloxy)propanal Darstellung aller vier stereoisomeren (1,2‐Dihydroxy‐[1‐2H1]propyl)phosphonsäuren aus chiralen Lactaten

Addition of Dialkyl Phosphites and Dialkyl Trimethylsilyl Phosphites to 2‐(Benzyloxy)propanal – Preparation of all Four Stereoisomeric (1,2‐Dihydroxy‐[1‐2H1]propyl)phosphonic Acids from Chiral LactatesDimethyl 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 diisopropyl phosphite. Starting from chiral lactates all four stereoisomeric diisopropyl (2‐benzyloxy‐1‐hydroxy‐[1‐2H1]phosphonates were prepared and deprotected. The (1,2‐dihydroxy‐[1‐2H1]propyl)phosphonic acids formed were purified as cyclohexylammonium salts. The relative configuration of phosphonic acid of (−)‐11 was determined by comparison with the salt (1R,2R)‐12 derived from fosfomycin.

The Simple Synthesis of Tetra-Alkyl Sym-Monothiopyrophosphates

Abstract This poster is a part of our continuing interest in the synthesis and properties of phosphorus acid anhydride analogs, particulary those containing sulfur bridge between two phosphorus atoms (1). Recently we have found that sulfur dichloride reacts with dialkyl trimethylsilyl phosphites 1 to form the tetra-alkyl sym-monothiopyrophosphates 2 in high yield.

ChemInform Abstract: Reaction of Oxophosphorane‐Sulfenyl and ‐Selenenyl Chlorides with Dialkyl Trimethylsilyl Phosphites. Novel Synthesis of Compounds Containing a Sulfur or Selenium Bridge Between Two Phosphoryl Centers.

AbstractThe novel highly efficient synthesis of the sym‐tetraalkyl monothio‐ and monoseleno‐pyrophosphates such as (III) and (V) based on the condensation of the phosphites (II) with the dialkoxyoxophosphorane‐sulfenyl or ‐selenenyl chlorides generated in situ from the silyl thio‐ or selenophosphates (I) and (IV).

ChemInform Abstract: Reaction of Diphosphoryl Diselenides with Dialkyl Trimethylsilyl Phosphites. A New Route to Symmetrical Monoselenopyrophosphates.

ChemInformVolume 19, Issue 36 Organoelement Compounds ChemInform Abstract: Reaction of Diphosphoryl Diselenides with Dialkyl Trimethylsilyl Phosphites. A New Route to Symmetrical Monoselenopyrophosphates. R. DEMBINSKI, R. DEMBINSKI Polish Acad. Sci., Centre Mol. Macromol. Stud., 90-362 Lodz, PolandSearch for more papers by this authorE. KRAWCZYK, E. KRAWCZYK Polish Acad. Sci., Centre Mol. Macromol. Stud., 90-362 Lodz, PolandSearch for more papers by this authorA. SKOWRONSKA, A. SKOWRONSKA Polish Acad. Sci., Centre Mol. Macromol. Stud., 90-362 Lodz, PolandSearch for more papers by this author R. DEMBINSKI, R. DEMBINSKI Polish Acad. Sci., Centre Mol. Macromol. Stud., 90-362 Lodz, PolandSearch for more papers by this authorE. KRAWCZYK, E. KRAWCZYK Polish Acad. Sci., Centre Mol. Macromol. Stud., 90-362 Lodz, PolandSearch for more papers by this authorA. SKOWRONSKA, A. SKOWRONSKA Polish Acad. Sci., Centre Mol. Macromol. Stud., 90-362 Lodz, PolandSearch for more papers by this author First published: September 6, 1988 https://doi.org/10.1002/chin.198836272Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume19, Issue36September 6, 1988 RelatedInformation

ChemInform Abstract: Reaction of Aryl Bromides with Dialkyl Trimethylsilyl Phosphites in the Presence of Nickel Chloride.

ChemInform Abstract: Reaction of Aryl Bromides with Dialkyl Trimethylsilyl Phosphites in the Presence of Nickel Chloride.

REACTION OF DIPHOSPHORYL DISELENIDES WITH DIALKYLTRIMETHYLSILYL PHOSPHITES. A NEW ROUTE TO SYMMETRICAL MONOSELENOPYROPHOSPHATES

Abstract A novel efficient synthesis of sym-monoselenopyrophosphates 3 based on the reaction of diphosphoryl diselenides 1 with dialkyltrimethylsilyl phosphites 2 is described.

Reaction of oxophosphorane-sulphenyl and -selenenyl chlorides with dialkyl trimethylsilyl phosphites. Novel synthesis of compounds containing a sulphur or selenium bridge between two phosphoryl centres

A novel highly efficient synthesis of sym-tetra-alkyl monothio- and monoseleno-pyrophosphates (RO)2P(O)XP(O)(OR′)2(X = S,Se) based on the condensation of dialkoxyoxophosphorane-sulphenyl or -selenenyl chlorides (RO)2P(O)XCl (X = S,Se) with dialkyl trimethylsilyl phosphites (RO)2POSiMe3(9) is described. Remarkably selective reaction of a O,O′-dialkyl O″-trimethylsilyl selenophosphate (RO)2P(Se)OSiMe3(13) with sulphuryl dichloride in the presence of an equimolar amount of a phosphite (9) leads to the formation of sym-monoselenopyrophosphates in excellent yield. A new rearrangement in phosphorus chemistry, sym-monoselenopyraphosphates (11) to asym-monoselenopyrophosphates (12), has been observed.

ChemInform Abstract: Synthesis of Symmetrical Tetra‐alkyl Monoselenopyrophosphates: Compounds Containing a Selenium Bridge between Two Phosphoryl Centres.

AbstractThe dialkyltrimethylsilyl selenophosphates (I) react with the dialkyltrimethylsilyl phosphites (II) in the presence of sulfuryl chloride, producing the selenopyrophosphates (III).

Novel synthesis of symmetrical tetra-alkyl monothiopyrophosphates

The novel highly efficient synthesis of sym-tetra-alkyl monothiopyrophosphates (RO) 2P(O)SP(O) (OR′) 2 1 based on the condensation of dialkoxyoxophosphoranesulphenyl chlorides 3 with dialkyltrimethylsilyl phosphites 4 is described.

Acylphosphonates. 6. Reaction mechanism of Zn/Me 3SiCl mediated conversion of 2,2,2-trichloroethoxycarbonylphosphonates to silyl phosphites

It was elucidated by 31P nmr spectroscopy that the conversion of 2,2,2-trichloroethoxycarbonylphosphonates to dialkyl trimethylsilyl phosphites by treatment with Me 3SiCl-Zn-acetylacetone proceed with retention configuration at phosphorus. In this study, optical active dinucleoside 2,2,2-trichloroethoxycarbonylphosphonates were synthesized and employed as the reaction substrates.

Synthesis of symmetrical tetra-alkyl monoselenopyrophosphates: compounds containing a selenium bridge between two phosphoryl centres

The remarkably selective reaction of O,O,O-dialkyltrimethylsilylselenophosphates (1) in the presence of equimolar amounts of dialkyltrimethylsilyl phosphites (2) with sulphuryl chloride leading to tetra-alkyl symmetrical selenopyrophosphates (3) in excellent yields is reported.

ChemInform Abstract: REACTION OF DIALKYL TRIMETHYLSILYLPHOSPHITES WITH CARBON TETRACHLORIDE

Chemischer InformationsdienstVolume 16, Issue 8 Organoelement Compounds ChemInform Abstract: REACTION OF DIALKYL TRIMETHYLSILYLPHOSPHITES WITH CARBON TETRACHLORIDE T. KH. GAZIZOV, T. KH. GAZIZOVSearch for more papers by this authorL. N. USMANOVA, L. N. USMANOVASearch for more papers by this authorD. V. RYZHIKOV, D. V. RYZHIKOVSearch for more papers by this authorA. N. PUDOVIK, A. N. PUDOVIKSearch for more papers by this author T. KH. GAZIZOV, T. KH. GAZIZOVSearch for more papers by this authorL. N. USMANOVA, L. N. USMANOVASearch for more papers by this authorD. V. RYZHIKOV, D. V. RYZHIKOVSearch for more papers by this authorA. N. PUDOVIK, A. N. PUDOVIKSearch for more papers by this author First published: February 26, 1985 https://doi.org/10.1002/chin.198508254Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume16, Issue8February 26, 1985 RelatedInformation