51549-40-7Relevant academic research and scientific papers
223. Phosphoramidites of Chiral (RP)- and (SP)-Configurated d(T-A): Synthesis, Configurational Assignment, and Use as Dimer Blocks in Oligonucleotide Synthesis
Herdering, Wilhelm,Kehne, Andreas,Seela, Frank
, p. 2119 - 2127 (1985)
The N,N-diisopropylphosphoramidites 10a and 10b of appropriately protected chiral diastereoisomers of d(T>P-18O>-A) (8a and 8b, resp.), chiral by virtue of the isotope 18O at the P-atom, have been synthesized.The 18O-isotope was incorporated by oxidation of the phosphite triester 3 with H2/I2.Separation of the diastereoisomers was accomplished by flash chromatography of the O-3'-deprotected phosphate triesters 5a/b.The absolute configuration at the chiral P-atom was deduced from the methylation products of the fully deprotected diastereoisomers 8a and 8b.Phosphinylation of 5a and 5b yielded the configurationally pure phosphoramidites 10a and 10b, respectively, which were then employed in solid-phase synthesis to yield the self-complementary oligomers d(G-A-G-T-(RP)--A-C-T-C) (13) and d(G-A-G-T-(SP)--A-C-T-C) (14), respectively.
Phosphoramidite nucleoside derivative as well as synthesis method, application and kit thereof
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, (2022/04/15)
The invention discloses a phosphoramidite nucleoside derivative as well as a synthesis method, application and a kit thereof, and belongs to the field of oligonucleotides. The synthesis method comprises the following steps: protecting hydroxyl of an initiator, protecting N6-site amino on a basic group, and then removing protection of 3 'and 5' hydroxyl to obtain a first intermediate; protecting 5'and 3 'hydroxyl groups of the first intermediate to obtain a second intermediate; removing a protecting group of 5'hydroxyl of the second intermediate, and protecting the 5 'hydroxyl through methoxy isopropyl to obtain a third intermediate; sequentially removing protecting groups of 3'hydroxyl and N6 amino on the basic group in the third intermediate to obtain a fourth intermediate; and carrying out imidization protection on an N6-site amino group on a basic group of the fourth intermediate, and carrying out phosphoramidation protection on a 3 '-hydroxyl group. The method has the advantages of being convenient to implement, economical and capable of achieving large-scale production.
Enantiodivergent Formation of C-P Bonds: Synthesis of P-Chiral Phosphines and Methylphosphonate Oligonucleotides
Baran, Phil S.,Eastgate, Martin D.,Knouse, Kyle W.,Padial, Natalia M.,Rivas-Bascón, Nazaret,Schmidt, Michael A.,Vantourout, Julien C.,Xu, Dongmin,Zheng, Bin
, (2020/03/30)
Phosphorus Incorporation (PI, abbreviated Π) reagents for the modular, scalable, and stereospecific synthesis of chiral phosphines and methylphosphonate nucleotides are reported. Synthesized from trans-limonene oxide, this reagent class displays an unexpected reactivity profile and enables access to chemical space distinct from that of the Phosphorus-Sulfur Incorporation reagents previously disclosed. Here, the adaptable phosphorus(V) scaffold enables sequential addition of carbon nucleophiles to produce a variety of enantiopure C-P building blocks. Addition of three carbon nucleophiles to Π, followed by stereospecific reduction, affords useful P-chiral phosphines; introduction instead of a single methyl group reveals the first stereospecific synthesis of methylphosphonate oligonucleotide precursors. While both Π enantiomers are available, only one isomer is required - the order of nucleophile addition controls the absolute stereochemistry of the final product through a unique enantiodivergent design.
CYCLIC DINUCLEOTIDES AS STING AGONISTS
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, (2019/07/19)
Disclosed are compounds, compositions and methods for treating of diseases, syndromes, or disorders that are affected by the modulation of STING. Such compounds are represented by Formula (I) as follows: wherein B2,X2, R2a, R2b, R2c, Z-M-Y, Y1-M1Z1, B1, X1, R1a, R1b, R1c are as defined herein.
C5′-adenosinyl radical cyclization. A stereochemical investigation
Navacchia, Maria Luisa,Chatsilialoglu, Chryssostomos,Montevecchi, Pier Carlo
, p. 4445 - 4452 (2007/10/03)
A variety of substituted 2′-deoxyadenosin-5′-yl radicals 3 were generated under different reaction conditions. Radicals 3 underwent intramolecular cyclization onto the C8-N7 double bond of the adenine moiety leading to aminyl radicals (5′S,8R)-4 and (5′R,8R)-4 and, eventually, to the corresponding cyclonucleosides 5 and 6. The effect of the solvent, the nature of the substituents, and the generation method of radicals 3 on the stereoselectivity of the C5′-radical cyclization have been considered. The observed increase of the (5′S)/(5′R) ratio by increasing the bulkiness of the R1 group is explained in terms of steric repulsion between R1 and the purine moiety which favors the C5′-endo conformation, whereas the effect of the water solvent in promoting the (5′R)-stereoselective cyclization is ascribed to intermolecular hydrogen bonding stabilizing the C5′-exo confomation.
Design, efficient synthesis, and anti-HIV activity of 4′-C-cyano- and 4′-C-ethynyl-2′-deoxy purine nucleosides
Kohgo, Satoru,Yamada, Kohei,Kitano, Kenji,Iwai, Yuko,Sakata, Shinji,Ashida, Noriyuki,Hayakawa, Hiroyuki,Nameki, Daisuke,Kodama, Eiichi,Matsuoka, Masao,Mitsuya, Hiroaki,Ohrui, Hiroshi
, p. 671 - 690 (2007/10/03)
Some 4′-C-ethynyl-2′-deoxy purine nucleosides showed the most potent anti-HIV activity among the series of 4′-C-substituted 2′-deoxynucleosides whose 4′-C-substituents were methyl, ethyl, ethynyl and so on. Our hypothesis is that the smaller the substitue
Facile and highly selective 5′-desilylation of multisilylated nucleosides
Zhu, Xue-Feng,Williams, Howard J.,Ian Scott
, p. 2305 - 2306 (2007/10/03)
The facile and highly selective 5′-desilylation of multisilylated nucleosides was discussed. The selective 5′-desilylation using aqueous acetic acid can be improved if THF is added as a co-solvent. It was found that the use of THF increases the solubility
Efficient procedure for the synthesis of 3'-O-t-butyldimethylsilyl-2'-deoxynucleosides
Patil, Sucheta V.,Mane, Ramchandra B.,Salunkhe, Manikrao M.
, p. 1 - 2 (2007/10/02)
3'-O-t-Butyldimethylsilyl-2'-deoxynucleosides (3) have been synthesized in high yields by the reaction of 5'-O-DMT-2'-deoxynucleosides (1) with t-butyldimethylsilyl chloride (TBDMS-Cl) in THF using butyllithium followed by detritylation with 80percent aq.
Synthesis and separation of diastereoisomers of O-(2,2,2-trifluoroethyl)-3',5'-dinucleoside phosphates
Luo,Atrazheva,Fregeau,Gmeiner,Lown
, p. 1548 - 1555 (2007/10/02)
The synthesis, diastereomeric separation, and characterization are described for a series of novel O-(2,2,2-trifluoroethyl)-3',5'-dinucleoside phosphates, required for incorporation into antisense probes in the magnetic resonance imaging investigation of
A facile method for detritylation of 5'-O-dimethoxy-trityl-3'-O-tert-butyldimethylsilyl-2'-deoxynucleosides
Patil,Mane,Salunkhe
, p. 2423 - 2428 (2007/10/02)
The dimethoxytrityl group can be removed effectively from 5'-O-dimethoxytrityl-3'-O-tert-butyl dimethylsilyl-2'-deoxynucleosides and their N-acyl derivatives by using sulfonated crosslinked (1% DVB) polystyrene in dichloromethane-methanol (97.5:2.5, v/v)
