34311-02-9Relevant academic research and scientific papers
REASSIGNMENT OF CONFIGURATIONS FOR 5-BROMO-2,3-DIOXABICYCLOHEPTANES AND ITS MECHANISTIC IMPLICATIONS
Bloodworth, A. J.,Eggelte, H. J.
, p. 169 - 172 (1981)
The configuration of the 5-bromo-2,3-dioxabicycloheptane obtained by treating 3,4-dibromocyclopentyl hydroperoxide with AgO2CCF3 and that of the isomer obtained using Ag2O have been reassigned after identifying which 4-bromocyclopentane-1,3-diol is obtained from each upon catalytic hydrogenation.This implies a bromonium ion mechanism for the AgO2CCF3-induced dioxabicyclization in contrast to the SN2-type displacements found for related compounds.
Synthesis of the Phosphonate Isostere of Carbocyclic 5-Bromovinyldeoxyuridine Monophosphate
Coe, Diane M.,Garofalo, Antonio,Roberts, Stanley M.,Storer, Richard,Thorpe, Andrew J.
, p. 3061 - 3064 (1994)
The nucleotide analogue 5 has been synthesized, via formation of the diol 11, and has been shown to be inactive against HSV in vitro.Resolution of the intermediate diol 11 was effected using a highly stereoselective enzyme-catalysed acetylation.
4'-PHOSPHATE ANALOGS AND OLIGONUCLEOTIDES COMPRISING THE SAME
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Paragraph 00366, (2018/03/25)
Disclosed herein are oligonucleotides, such as nucleic acid inhibitor molecules, having a 4'-phosphate analog and methods of using the same, for example, to modulate the expression of a target gene in a cell. The phosphate analogs are bound to the 4'-carbon of the sugar moiety (e.g., a ribose or deoxyribose or analog thereof) of the 5'-terminal nucleotide of an oligonucleotide. Typically, the phosphate analog is an oxymethylphosphonate, where the oxygen atom of the oxymethyl group is bound to the 4'-carbon of the sugar moiety or analog thereof.
Preparation of carbocyclic analogues of 2'-deoxyribonucleotides possessing a phosphonate substituent at the 5'-position
Drake, Alex F.,Garofalo, Antonio,Hillman, Jennifer M. L.,Merlo, Valeria,McCague, Ray,Roberts, Stanley M.
, p. 2739 - 2746 (2007/10/03)
The epoxycyclopentanol 10 is converted into the methylphosphonate 15 in 30percent overall yield.The diol 15 is converted into the protected carbocyclic nucleotide mimics 16, 18, 21 and 22 in 38-70 percent yield.The diol 15 is resolved using a lipase-catal
Prostaglandin Endoperoxide Model Compounds. Part 2. Stereospecific Synthesis of Isomeric 5-Bromo-2,3-dioxabicycloheptanes and 2-Bromo-6,7-dioxabicyclooctanes
Bloodworth, A. J.,Eggelte Henny J.
, p. 3272 - 3278 (2007/10/02)
Cyclopent-3-enyl hydroperoxide (9) has been prepared from cyclopentadiene via hydroboration and autoxidation, and converted by bromination into trans-3,cis-4-dibromocyclopentyl hydroperoxide (10).Reaction of compound (10) with silver oxide has afforded endo-5-bromo-2,3-dioxabicycloheptane (11) (42percent), whereas treatment of compound (10) with silver trifluoroacetate has provided exo-5-bromo-2,3-dioxabicycloheptane (15) (6percent) and exo-5-trifluoroacetoxy-2,3-dioxabicycloheptane (16) (14percent).The exo-bromide (15) (11percent) has also been prepared from cyclopent-3-enyl bromide by trans-hydroperoxybromination and ring closure with silver oxide.The configurations of the peroxides have been confirmed by catalytic hydrogenation.Cyclohex-3-enyl hydroperoxide (26) has been prepared from anisole by a 5-step procedure ending with oxidation of N-cyclohex-3-enyl-N'-tosylhydrzide, and converted by bromination into a mixture of two diastereoisomeric 3,4-dibromocyclohexyl hydroperoxides.Treatment of the trans-3,cis-4-dibromide (27) with silver oxide has afforded endo-2-bromo-6,7-dioxabicyclooctane (29) (40percent), whereas reaction of the cis-3,trans-4-dibromide (28) with silver trifluoroacetate has provided exo-2-bromo-6,7-dioxabicyclooctane (30) (18percent).Treatment of compound (27) with silver trifluoroacetate yielded a 9:1 mixture of peroxides (30) and (29) (19percent), but compound (28) did not react with silver oxide.It is suggested that the silver oxide-induced dioxabicyclizations proceed by an SN2 mechanism whereas the silver trifluoroacetate reactions involve a bromonium ion intermediate.
