185556-78-9

Basic information

• Product Name: (Z)-2'-deoxy-2'-ethoxycarbonylmethylene-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)uridine
• Synonyms: (Z)-2'-deoxy-2'-ethoxycarbonylmethylene-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)uridine;(Z)-ethyl 2-((6aR,8R,9aS)-8-(2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl)-2,2,4,4-tetraisopropyl-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-9(6aH,8H,9aH)-ylidene)acetate;(Z)-ethyl 2-((6aR,8R,9aS)-8-(2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl)-2,2,4,4-tetraisopropyl-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-9(6aH,8H,9aH)-ylidene)acetate(WXC03691)
• CAS NO: 185556-78-9
• Molecular Formula: C₂₅H₄₂N₂O₈Si₂
• Molecular Weight: 554.78058
• Mol File: 185556-78-9.mol
• Article Data: 1

Chemical Properties

• Appearance: /
• CAS DataBase Reference: (Z)-2'-deoxy-2'-ethoxycarbonylmethylene-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)uridine(CAS DataBase Reference)
• NIST Chemistry Reference: (Z)-2'-deoxy-2'-ethoxycarbonylmethylene-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)uridine(185556-78-9)
• EPA Substance Registry System: (Z)-2'-deoxy-2'-ethoxycarbonylmethylene-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)uridine(185556-78-9)

Safety Data

• Hazardous Substances Data: 185556-78-9(Hazardous Substances Data)

Upstream product

• 84828-97-7 1-((6aR,8R,9aR)-2,2,4,4-tetraisopropyl-9-oxotetrahydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-8-yl)pyrimidine-2,4(1H,3H)-dione 
• 1099-45-2 ethyl (triphenylphosphoranylidene)acetate 

Downstream Products

• 185556-84-7 1-((3aS,4R,6R,6aR)-2-Oxo-3a-phenylsulfanyl-6-triisopropylsilanyloxymethyl-hexahydro-furo[3,4-b]furan-4-yl)-1H-pyrimidine-2,4-dione 

Relevant articles and documents

Nucleosides and Nucleotides. 156. Chelation-Controlled and Nonchelation-Controlled Diastereofacial Selective Thiophenol Addition Reactions at the 2′-Position of 2′-[(Alkoxycarbonyl)methylene]-2′-deoxyuridines: Conversion of (Z)-2′-[(Alkoxycarbonyl)methylene]-2′-deoxyuridines into Their (E)-Isomers

The Wittig reaction of 1-[3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-β-D-erythro- pentofuranos-2-ulosyl]uracil (4) with Ph3P=CHCO2R (R = ethyl or tert-butyl) exclusively gave (Z)-2′-[(alkoxycarbonyl)methylene] derivatives 5 and 13, respectively, in high yields. An unusual β-facial selectivity of thiophenol addition to the 2′-[(alkoxycarbonyl)methylene] moiety of 5 and 13 was observed, and this facial selectivity was found to be influenced by both the thiolate counter cation and the bulkiness of the alkoxy moiety. Treatment of 2′-[(ethoxycarbonyl)methylene] derivative 5 with LiSPh (1.5 equiv) in the presence of PhSH in THF selectively gave 2′β-(phenylthio) derivative 11 in high yield along with a trace of 2'α-(phenylthio) derivative 10. On the other hand, when 2′-[(tert-butoxycarbonyl)methylene] derivative 13 was treated with KSPh in the presence of PhSH in dioxane/DMF, the facial selectivity was reversed to selectively give the 2′α-(phenylthio) adduct 14 (α:β, 77:23) in 90% yield. Oxidation of 14 with m-chloroperbenzoic acid in CH2Cl2 and subsequent pyrolysis of the resulting sulfoxides exclusively gave the (Z)-isomer 13 in 92% yield. The oxidative syn-elimination of the (2′R)-2′-[(tert-butoxycarbonyl)methyl]-2′-deoxy-2′- thiophenoxy-5′-O-(triisopropylsilyl)uridine (17), which was obtained from 14 in two steps, exclusively gave the desired (E)-[(tert-butoxycarbonyl)methylene] derivatives 18 in 90% yield. Deprotection of 18 gave the (E)-(carboxymethylene)-2′-deoxyuridine (3). The (Z)-(carboxymethylene)-2′-deoxyuridine (2) was synthesized from 13 in a similar manner.