14422-01-6

Upstream product

• 177748-70-8 2-Allyl-thiobenzoic acid S-[2-(2-iodo-phenyl)-2-methyl-propyl] ester 
• 67-56-1 methanol 
• 470700-02-8 5'-O-benzyl-4'α-[(2-(2-bromophenyl)-2-methylpropylthio)carbonyl]-2'-deoxy-3'-O-diethylphosphoryladenosine 
• 470699-98-0 5'-O-benzyl-4'α-[(2-(2-bromophenyl)-2-methylpropylthio)carbonyl]-2'-deoxy-3'-O-diethylphosphorylthymidine 
• 470700-00-6 5'-O-benzyl-4'α-[(2-(2-bromophenyl)-2-methylpropylthio)carbonyl]-2'-deoxy-3'-O-diethylphosphorylcytidine 
• 177748-69-5 2-Allyloxy-thiobenzoic acid S-[2-(2-iodo-phenyl)-2-methyl-propyl] ester 
• 24850-33-7 allyltributylstanane 

Downstream Products

• 123065-78-1 methyl (E)-4-<2-(2,3-dihydro-3,3-dimethylbenzothien-5-yl)-1-propenyl>benzoate 
• 132102-36-4 <1-(2,3-dihydro-3,3-dimethylbenzothien-5-yl)ethyl>triphenylphosphonium bromide 
• 123065-77-0 (E)-4-[2-(2,3-dihydro-3,3-dimethylbenzo[b]thien-5-yl)-1-propenyl]benzoic acid 

Relevant academic research and scientific papers

The effect of the base in the fragmentation of nucleotide C4′ radicals

A series of 3′-O-diethylphosphoryl-4′-α-[(2-halophenylethylthio) carbonyl] substituted esters of thymidine, cytidine, adenosine and guanosine are prepared by total synthesis and used as C4′-radical precursors in a competition kinetic method using tributyltin hydride as the reductant. The pseudo-first order rate constants for the C4′-radicals so generated decrease in the order guansoine>cytidine>adenosine>thymidine with that for guanosine being too rapid for determination by the present competition kinetic method. A 119Sn NMR method is presented for estimation of the purity of tin hydride solutions.

Free radical chemistry of nucleosides and nucleotides. Ring opening of C4'-radicals

It is demonstrated that nucleotide C4' radicals may be generated from a C4'-thiolester on treatment with tributyltin hydride. When the reaction is conducted in benzene at reflux the C4' radical expels the C3'-phosphate group to give a radical cation. This species undergoes deprotonation to an allylic radical which suffers cleavage of the deoxyribose ring. Similar reactions are observed when the reaction is conducted with tris(trimethylsilyl)silane in place of the stannane. In methanolic benzene the radical cation is trapped by methanol to give a new C4' radical which is quenched before ring opening. The behavior of C4' radicals toward ring opening is discussed in terms of the conformations imposed by the substituents at C3'.