ABSTRACT
A new, efficient method is developed, based on a palladium(0)-catalyzed reaction of propargylic derivatives with various phosphorus nucleophiles, to produce allenylphosphonates and their analogues with defined stereochemistry in the allenic and the phosphonate moiety.
Subject(s)
Alkadienes/chemistry , Palladium/chemistry , Phosphates/chemical synthesis , Phosphorus/chemistry , Catalysis , Molecular Structure , StereoisomerismABSTRACT
tert-Butyldithiomethyl (DTM), a novel hydroxyl protecting group, cleavable under reductive conditions, was developed and applied for the protection of 2'-OH during solid-phase RNA synthesis. This function is compatible with all standard protecting groups used in oligonucleotide synthesis, and allows for fast and high-yield synthesis of RNA. Oligonucleotides containing the 2'-O-DTM groups can be easily deprotected under the mildest possible aqueous and homogeneous conditions. The preserved 5'-O-DMTr function can be used for high-throughput cartridge RNA purification.
Subject(s)
Alkanes/chemistry , RNA/chemical synthesis , Sulfur Compounds/chemistry , Alkanes/chemical synthesis , RNA/isolation & purification , Sulfur Compounds/chemical synthesisABSTRACT
2-,3-,4-Pyridylphosphonates and their phosphonothioate congeners were analyzed by electrospray ionization multistage tandem mass spectrometry (ESI-MS(n)). It was found that the fragmentation pathways of these compounds were not influenced to any detectable extent by the stereochemistry at the phosphorus centers but were sensitive to the position of a nitrogen atom in the pyridine ring of these compounds. Possible mechanisms for fragmentations of the investigated compounds are discussed in detail.
Subject(s)
Nitrogen/chemistry , Nucleosides/chemistry , Organophosphorus Compounds/chemistry , Spectrometry, Mass, Electrospray Ionization/methods , Dimerization , Molecular Conformation , Sensitivity and Specificity , StereoisomerismABSTRACT
In this paper a short account of our recent basic studies aiming toward development of new synthetic methods for the preparation of nucleotide analogues using H-phosphonate chemistry is presented.
Subject(s)
Nucleotides/chemical synthesis , Organophosphonates/chemistry , Phosphorus Compounds/chemical synthesis , Phosphorus/chemistry , Models, Chemical , Nucleosides/chemistry , Nucleotides/chemistry , StereoisomerismABSTRACT
In this paper a short account of our recent research concerning the development of new synthetic methods and reagents for the preparation of nucleotides and their analogues, is given.
Subject(s)
Nucleosides/chemistry , Organophosphonates/chemistry , Sulfhydryl Compounds/chemistry , Models, Molecular , Nucleosides/chemical synthesis , Nucleotides/chemical synthesis , Nucleotides/chemistryABSTRACT
An efficient and stereospecific synthesis of dinucleoside 4'-(2,2':6',2''-terpyridyl)phosphonate 2 and 5-(2,2'-bipyridyl)phosphonate 3 via a palladium(0) cross coupling strategy has been developed.
