130446-03-6

Upstream product

• 124-63-0 methanesulfonyl chloride 
• 42926-80-7 5'-O-(4-monomethoxytrityl)-2'-deoxythymidine 
• 50-89-5 thymidine 
• 14470-28-1 mono-4-methoxytrityl chloride 

Downstream Products

• 124680-50-8 (1R,9R,10R)-10-[[(4-methoxyphenyl)diphenyl]methoxymethyl]-4-methyl-8,11-dioxa-2,6-diazatricyclo[7.2.1.0^2,7]dodeca-3,6-dien-5-one 
• 142827-05-2 C₆₀H₅₈N₄O₁₀S₂ 
• 119009-80-2 C₄₅H₄₈N₅O₁₃PS 
• 119005-68-4 5′-O-(mono-p-methoxytriphenylmethyl)-3′-deoxy-3′-thiothymidine 
• 177084-36-5 Hexadecanoic acid 2-{[(2S,3S,5R)-3-azido-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-2-ylmethoxy]-[2-(4-nitro-phenyl)-ethoxy]-phosphoryloxy}-1-hexadecanoyloxymethyl-ethyl ester 
• 177084-37-6 Tetradecanoic acid 2-{[(2S,3S,5R)-3-azido-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-2-ylmethoxy]-[2-(4-nitro-phenyl)-ethoxy]-phosphoryloxy}-1-tetradecanoyloxymethyl-ethyl ester 
• 177084-38-7 Phosphoric acid (2S,3S,5R)-3-azido-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-2-ylmethyl ester 2,3-bis-hexadecyloxy-propyl ester 2-(4-nitro-phenyl)-ethyl ester 
• 30516-87-1 3'-azido-2',3'-deoxythymidine 
• 339178-42-6 (2R,4R,5R)-1-[5-[bis(4-methoxyphenyl)phenylmethoxymethyl]-4-(tert-butyldiphenylsilanyloxy)tetrahydrofuran-2-yl]-5-methyl-1H-pyrimidine-2,4-dione 
• 339178-44-8 (2S,3R,5R)-3-(tert-butyldiphenylsilanyloxy)-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)tetrahydrofuran-2-carboxylic acid 
• 339178-45-9 (2S,3R,5R)-3-(tert-butyldiphenylsilanyloxy)-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)tetrahydrofuran-2-carboxylic acid methyl ester 
• 339178-43-7 (2R,4R,5R)-1-[4-(tert-butyldiphenylsilanyloxy)-5-hydroxymethyltetrahydrofuran-2-yl]-5-methyl-1H-pyrimidine-2,4-dione 
• 339178-34-6 (2R,3R,5R)-3-hydroxy-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-2-(phenylselenenyl)tetrahydrofuran-2-carboxylic acid methyl ester 
• 339269-55-5 1-((2R,4R,5S)-4-hydroxy-5-hydroxymethyl-5-phenylselenenyltetrahydrofuran-2-yl)-5-methyl-1H-pyrimidine-2,4-dione 

Relevant academic research and scientific papers

METHOD FOR PREPARING 3'-O-AMINO-2'-DEOXYRIBONUCLEOSIDE-5'-TRIPHOSPHATE

The invention relates to a method for preparing 3 ' -O-amino-2' -deoxyribonucleoside-5 ' - triphosphate. It also relates to a solid support functionalized with at least one N- hydroxyphthalimide moiety and uses thereof for protecting 3 '-hydroxy group of a 2'- deoxyribonucleoside during synthesis of a nucleoside or a derivative thereof.

Preparation of 4'-substituted thymidines by substitution of the thymidine 5'-esters.

tert-Butyl thymidylate 3 was prepared from thymidine 1 in six steps and 67% overall yield. When the lithium trianion of 3 (prepared by treatment of 3 with excess LDA and then excess tert-butyllithum) is reacted with electrophiles, trapping occurs stereoselectively from either the alpha- or beta-face depending on the electrophile (Scheme 1). Deuterioacetic acid in deuteriomethanol affords mainly the alpha-deuterated product (4a/4b = 2.4:1) while all other electrophiles, e.g., phenylselenenyl chloride, allyl bromide, and N-fluorobenzenesulfonimide (NFSI), give predominately (or completely) the products of attack from the beta-face (5bcd/4bcd = 3.7:1 to 100:0). The structures of the products were determined by coupling constant analysis of both the initial compounds and the diols 6bcd prepared by ester reduction and by formation of the acetonides 7bc. The methyl ester of the 3'-epimer of thymidylic acid 9 was also prepared from thymidine 1 in nine steps and 74% overall yield. When the lithium trianion of 9 (prepared by treatment of 9 with excess LDA and then excess tert-butyllithum) is reacted with electrophiles, trapping also occurs stereoselectively with attack on either the alpha- or beta-face depending on the electrophile (Scheme 2). Again, deuterioacetic acid in deuteriomethanol affords mainly the beta-deuterated product (11a/10a = 1.6:1) while all other electrophiles, e.g., phenylselenenyl chloride, methyl iodide, allyl bromide, and NFSI, gave predominately (or completely) the product of attack from the alpha-face (8.7:1 to 100: 0). Again, the structures of the products were determined by coupling constant analysis of both the initial compounds, and the diols 12b-e were prepared by reduction of the ester and by formation of the acetonides 13bcd. A rationale has been developed using molecular mechanics calculations to explain the diastereoselectivity that involves staggered axial attack on the sp(2) carbon opposite to the pseudoaxial alkoxy group in the most stable half-chair conformation of the enolates, as shown in Schemes 3-5.

Incorporation of positively charged deoxynucleic S-methylthiourea linkages into oligodeoxyribonucleotides

Oligodeoxyribonucleic acids (15- and 18-mers) containing both negatively charged phosphate and positively charged S-methyl thiourea internucleoside linkages (DNmt/DNA chimera) have been synthesized. DNA binding characteristics and nuclease resistance of DNmt/DNA chimera have been evaluated.

38. Nucleotides: Part XLVI. The synthesis of phospholipid conjugates of antivirally active nucleosides by the improved phosphoramidite methodology

The application of the improved phosphoramidite strategy for the synthesis of oligonucleotides using β-eliminating protecting groups to phospholipid chemistry offers the possibility to synthesize phospholipid conjugates of AZT (6) and cordycepin. The synthesis of 3′-azido-3′-deoxythymidine (6) was achieved by a new isolation procedure without chromatographic purification steps in an overall yield of 50%. Protected cordycepin (=3′-deoxyadenosine) derivatives, the N6,2′-bis[2-(4-nitrophenyl)ethoxycarbonyl]cordycepin (12) and the N6,5′-bis[2-(4-nitrophenyl)ethoxycarbonyl]cordycepin (13) were prepared by known methods and direct acylation of N6-[2-(4-nitrophenyl)ethoxycarbonyl]cordycepin (9), respectively. These protected nucleosides and the 3′-azido-3′-deoxythymidine (6) reacted with newly synthesized and properly characterized lipid-phosphoramidites 21-25, catalyzed by 1H-tetrazole, to the corresponding nucleoside-phospholipid conjugates 26-38 in high yield. The deprotection was accomplished via β-elimination with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in aprotic solvents to give analytically pure nucleoside-phospholipid diesters 39-51 as triethylammonium or sodium salts. The newly synthesized compounds were characterized by elemental analyses and UV and 1H-NMR spectra.