A 400- and 600-MHz proton NMR conformational study on nucleoside cyclic 3',5' Pv-TBP systems. Conformational transmission induces diequatorial orientation of the 3',5'-dioxaphosphorinane ring in a nonchair conformation

Abstract

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Reactions of α-Diketones ando-Quinones with Phosphorus Compounds

“…cis -Thymidine 3‘,5‘-cyclic methyl phosphite ( 511 ) and cis -thymidine 3‘,5‘-cyclic 2-methoxyethyl phosphite ( 513 ) react with 1 equiv of tetrachloro-1,2-benzoquinone at −80 °C in dichloromethane to give the nucleoside cyclic 3‘,5‘ P v -trigonal bipyramidal (TBP) phosphorus compounds 512 and 514 . These products were studied as the model for the enzymatic and nonenzymatic reactions involving cyclic adenosine 3‘,5‘-monophosphite (cAMP).…”

Cyclic Aminophosphites and -phosphoranes Possessing Six- and Higher-Membered Rings: A Comparative Study of Structure and Reactivity

“…Cyclic oxyphosphoranes in which the pentacoordinated phosphorus is part of a six- or higher-membered ring have been the subject of intensive structural investigations during the past few years. − Structural studies on the corresponding cyclic phosphites, particularly those with a 1,3,2-dioxaphosphorinane ring, have been mainly limited to the solution state, except for one important study by Verkade and co-workers …”

Nucleoside 3′,5′-Cyclic H-Phosphonates, New Useful Precursors for the Synthesis of Nucleoside 3′,5′-Cyclic Phosphates and Their Analogues

“…15À17 All these methods are multistep and afford final nucleoside 3 0 ,5 0 -cyclic phosphotriesters in moderate or poor yield. 16,17 This can be a serious drawback when working with starting materials that are not readily accessible (e.g., antiviral nucleoside or nucleotide analogues) or with compounds for which diverse modifications at the phosphorus center are required.…”

“…From a synthetic point of view, different chemistries were applied for the preparation of nucleoside cyclic phosphotriesters. The most common approach involves condensation of the corresponding cyclic phosphodiesters with an alcohol aided by a condensing agent, or an alkylation reaction with a suitable alkylating agent. − Other methods make use of bifunctional phosphorylating reagents which, after phosphorylation of one hydroxyl group of a suitably protected nucleoside, form a 3′,5′ six-membered ring in a subsequent intramolecular cyclization reaction. − All these methods are multistep and afford final nucleoside 3′,5′-cyclic phosphotriesters in moderate or poor yield. , This can be a serious drawback when working with starting materials that are not readily accessible (e.g., antiviral nucleoside or nucleotide analogues) or with compounds for which diverse modifications at the phosphorus center are required.…”