129173-16-6Relevant academic research and scientific papers
D-arbinose-based synthesis of homo-C-d4T and homo-C-thymidine
Doboszewski, Bogdan
experimental part, p. 875 - 901 (2010/08/19)
2,3,5-Tri-O-benzyl-D-arabinofuranosyl halides (chloride, bromide) were reacted with AllMgBr, MeMgBr, and VinMgBr to furnish anomeric mixtures of the C-glycosyl products. The factors that influenced the β/α ratio are discussed. The α,β-C-vinyl derivative was transformed into 1-deoxy-1-C-hydroxymethyl-β and α-D-arabinofuranoses (2,5-anhydro-D-glucitol and -mannitol, respectively), separable after isopropylidenation step. 2,5-Anhydro-1,3-O-isopropylidene-D-glucitol was converted into 2,5-anhydro-6-O-triphenylmethyl-D-erythro-hex-3,4-enitol and 2,5-anhydro-4,6-di-O-benzoyl-3-deoxy-D-ribo-hexitol, which were coupled with N-3-benzoylthymine under the Mitsunobu conditions to furnish two analogs of nucleosides with a -CH2- insert between sugar moieties and thymine. (Chemical Equation Presented).
Highly stereoselective synthesis of C-vinyl furanosides through acid-catalyzed SN2 inversion at the C-3 position of 1,2-dideoxy-hept-1-enitols
Tsuchiya, Hitoshi,Asakura, Noriaki,Ikeda, Yasunori,Yamada, Hidetoshi
experimental part, p. 2985 - 2988 (2009/04/05)
A highly stereoselective synthesis of C-vinyl furanosides through the SN2 inversion at the C-3 position of the 1,2-dideoxy-hept-1-enitols is disclosed. Treatment of the 1,2-dideoxy-hept-1-enitols with diphenylammonium trifluoromethanesulfonate as the acid catalyst produced the C-vinyl furanosides (3,6-anhydro-1,2-dideoxy-hept-1-enitol derivatives) via a subsequent SN2 intramolecular debenzyloxyation-cycloetherification reaction at the C-3 position.
Syntheses of α- and β-C-glucopyranosyl serines from a common intermediate
Nolen, Ernest G.,Donahue, Laurence A.,Greaves, Rebecca,Daly, Trevor A.,Calabrese, David R.
scheme or table, p. 4911 - 4914 (2009/05/31)
(Chemical Equation Presented) A versatile synthesis leading to either C-linked α- or β-glucopyranosyl serines is presented from a common, advanced synthetic intermediate. Cyclization of the penultimate carbinol onto the alkene and methanolysis of the lactone yields selectively the α-linkage. A transposition of these last steps leads to the α-linked isomer selectively.
Synthesis of Selectively Labeled D-Fructose and D-Fructose Phosphate Analogues Locked in the Cyclic Furanose Form
Persky, Rachel,Albeck, Amnon
, p. 5632 - 5638 (2007/10/03)
2,5-Anhydroglucitol and 2,5-anhydromannitol and their 6-phosphate and 1,6-diphosphate derivatives are cyclic analogues of the α and β anomers of D-fructofuranose, D-fructofuranose-6-phosphate, and D-fructofuranose-1,6-diphosphate. They were synthesized from protected D-mannose or D-glucose. The synthetic method was developed with emphasis on selective 2H labeling of these compounds, as a model for 3H incorporation, which will be used for further biochemical studies. A key cyclization step, based on a benzyl ether nucleophilic attack on an activated alcohol, constructed the ring system. The stereochemistry at C2 (α/β anomers) and at C5 (D sugar) was controlled by selective epimerizations. Mono- and diphosphate analogues were obtained from the same intermediate by changing the sequence of deprotection and phosphorylation steps.
An unexpected rearrangement during Mitsunobu epimerization reaction of sugar derivatives
Persky, Rachel,Albeck, Amnon
, p. 3775 - 3780 (2007/10/03)
Mitsunobu reaction on the glucose derivative (3S,4R,5R,6R)-3,4,5,7- tetrabenzyloxy-6-hydroxy-1-heptene yielded an unexpected rearrangement major product. Its structure was determined as (3R,4R,5R,6S)-4,5,6,7- tetrabenzyloxy-3-hydroxy-1-heptene. The suggested rearrangement mechanism involves an initial intramolecular cyclization, followed by ring opening by the nucleophile p-nitrobenzoate. Product distribution of the Mitsunobu reaction was substrate-dependent, with the corresponding mannose derivative (the 3R epimer) giving less of the initial intramolecular reaction products and the corresponding galactose derivative (the 5S epimer) yielding almost exclusively the expected epimerization product. Varying the Mitsunobu reaction conditions (addition of base and using nonpolar solvent) led to the expected epimerization product of the glucose derivative.
Spontaneous cyclization of triflates derived from δ-benzyloxy alcohols: Efficient and general synthesis of C-vinyl furanosides
Martin, Olivier R.,Yang, Feng,Xie, Fang
, p. 47 - 50 (2007/10/02)
On reaction with triflic anhydride, the hept-1-enitols resulting from the Wittig reaction of tetra-O-benzyl D-hexopyranoses with [Ph3P=CH2] lead, in one step, to 3,6-anhydro-hept-1-enitol derivatives ('C-vinyl furanosides') in high y
