80734-73-2Relevant academic research and scientific papers
A Chiral Copper Catalyzed Site-Selective O-Alkylation of Carbohydrates
Ren, Bo,Wang, Jiaxi,Zhang, Mengyao,Chen, Yue,Zhao, Wei
supporting information, p. 665 - 670 (2021/12/02)
Highly regioselective alkylation of sugar hydroxyl groups has always been an important challenge in carbohydrate chemistry, especially for the selective alkylation of trans diols, there is no direct and efficient catalytic method so far. A chiral copper c
SnCl2-Catalyzed Acetalation/Selective Benzoylation Sequence for the Synthesis of Orthogonally Protected Glycosyl Acceptors
Dong, Hai,Feng, Guang-Jing,Guo, Yang-Fan,Liu, Chun-Yang,Lv, Jian
, (2022/04/03)
Based on SnCl2-catalyzed acetalation and selective benzoylation, a one-pot strategy to efficiently synthesize orthogonally protected glycosyl acceptors with 2-OH/3-OH was developed. Consequently, 2-OBz or 3-OBz 4,6-O-benzylidene galactosides and glucosides were efficiently prepared in moderate to high yields starting from free galactosides and glucosides, and were used as valuable glycosyl acceptors for the synthesis of blood group antigens O and B analogues in this study.
Regio/site-selective alkylation of substrates containing a: Cis -, 1,2- or 1,3-diol with ferric chloride and dipivaloylmethane as the catalytic system
Lv, Jian,Liu, Yu,Zhu, Jia-Jia,Zou, Dapeng,Dong, Hai
supporting information, p. 1139 - 1144 (2020/03/11)
In this study, we reported the regio/site-selective alkylation of substrates containing a cis-, 1,2- or 1,3-diol with FeCl3 as a key catalyst. A catalytic system consisting of FeCl3 (0.01-0.1 equiv.) and dipivaloylmethane (FeCl3/dipivaloylmethane = 1/2) was used to catalyze the alkylation in the presence of a base. The produced selectivities and isolated yields were similar to those obtained by methods using the same amount of FeL3 (L = acylacetone ligand) as the catalyst in most cases. The previously reported FeL3 catalysts for alkylation are not commercially available and have to be synthesized prior to use. In contrast, FeCl3 and dipivaloylmethane (Hdipm) are very common and inexpensive nontoxic reagents in the lab, thereby making the method much greener and easier to handle. Mechanism studies confirmed for the first time that FeCl3 initially reacts with two equivalents of Hdipm to form [Fe(dipm)3] in the presence of a base in acetonitrile, followed by the formation of a five or six-membered ring intermediate between [Fe(dipm)3] and two hydroxyl groups of the substrate. A subsequent reaction between the cyclic intermediate and the alkylating agent results in selective alkylation of the substrate.
Both d - And l -Glucose Polyphosphates Mimic d - myo-Inositol 1,4,5-Trisphosphate: New Synthetic Agonists and Partial Agonists at the Ins(1,4,5)P3Receptor
Shipton, Megan L.,Riley, Andrew M.,Rossi, Ana M.,Brearley, Charles A.,Taylor, Colin W.,Potter, Barry V. L.
, p. 5442 - 5457 (2020/07/21)
Chiral sugar derivatives are potential cyclitol surrogates of the Ca2+-mobilizing intracellular messenger d-myo-inositol 1,4,5-trisphosphate [Ins(1,4,5)P3]. Six novel polyphosphorylated analogues derived from both d- and l-glucose were synthesized. Binding to Ins(1,4,5)P3 receptors [Ins(1,4,5)P3R] and the ability to release Ca2+ from intracellular stores via type 1 Ins(1,4,5)P3Rs were investigated. β-d-Glucopyranosyl 1,3,4-tris-phosphate, with similar phosphate regiochemistry and stereochemistry to Ins(1,4,5)P3, and α-d-glucopyranosyl 1,3,4-tris-phosphate are full agonists, being equipotent and 23-fold less potent than Ins(1,4,5)P3, respectively, in Ca2+-release assays and similar to Ins(1,4,5)P3 and 15-fold weaker in binding assays. They can be viewed as truncated analogues of adenophostin A and refine understanding of structure-activity relationships for this Ins(1,4,5)P3R agonist. l-Glucose-derived ligands, methyl α-l-glucopyranoside 2,3,6-trisphosphate and methyl α-l-glucopyranoside 2,4,6-trisphosphate, are also active, while their corresponding d-enantiomers, methyl α-d-glucopyranoside 2,3,6-trisphosphate and methyl α-d-glucopyranoside 2,4,6-trisphosphate, are inactive. Interestingly, both l-glucose-derived ligands are partial agonists: they are among the least efficacious agonists of Ins(1,4,5)P3R yet identified, providing new leads for antagonist development.
One-pot synthesis of orthogonally protected sugars through sequential base-promoted/acid-catalyzed steps: A solvent-free approach with self-generation of a catalytic species
Traboni, Serena,Bedini, Emiliano,Giordano, Maddalena,Iadonisi, Alfonso
supporting information, p. 1777 - 1780 (2019/06/07)
A varied set of solvent-free, one-pot synthetic sequences were developed to carry out the orthogonal protection of saccharide polyols. These sequences are composed of an initial regioselective benzylation, silylation or iodination (under mildly basic cond
Synthesis and binding affinity analysis of α1-2- and α1-6-O/S-linked dimannosides for the elucidation of sulfur in glycosidic bonds using quartz crystal microbalance sensors
Norberg, Oscar,Wu, Bin,Thota, Niranjan,Ge, Jian-Tao,Fauquet, Germain,Saur, Ann-Kathrin,Aastrup, Teodor,Dong, Hai,Yan, Mingdi,Ramstr?m, Olof
supporting information, p. 35 - 42 (2017/10/25)
The role of sulfur in glycosidic bonds has been evaluated using quartz crystal microbalance methodology. Synthetic routes towards α1-2- and α1-6-linked dimannosides with S- or O-glycosidic bonds have been developed, and the recognition properties assessed in competition binding assays with the cognate lectin concanavalin A. Mannose-presenting QCM sensors were produced using photoinitiated, nitrene-mediated immobilization methods, and the subsequent binding study was performed in an automated flow-through instrumentation, and correlated with data from isothermal titration calorimetry. The recorded Kd-values corresponded well with reported binding affinities for the O-linked dimannosides with affinities for the α1-2-linked dimannosides in the lower micromolar range. The S-linked analogs showed slightly disparate effects, where the α1-6-linked analog showed weaker affinity than the O-linked dimannoside, as well as positive apparent cooperativity, whereas the α1-2-analog displayed very similar binding compared to the O-linked structure.
Highly Efficient Selective Benzylation of Carbohydrates Catalyzed by Iron(III) with Silver Oxide and Bromide Anion as Co-catalysts
Ren, Bo,Lv, Jian,Zhang, Yu,Tian, Jun,Dong, Hai
, p. 950 - 953 (2017/03/27)
A highly efficient, green, and regioselective method for the benzylation of diols and polyols was developed. With the use of Ag2O (0.6 equiv.) and tetrabutylammonium bromide (0.1 equiv.) as co-catalysts, the iron(III)-catalyzed benzylation reaction proceeded to completion at 40 °C within 2–3 h and gave the products in high yields with high regioselectivities. A mechanism involving the principle of enhanced basicity of Ag2O by soft anions was proposed.
Mild Method for 2-Naphthylmethyl Ether Protecting Group Removal Using a Combination of 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and β-Pinene
Lloyd, Dina,Bylsma, Marissa,Bright, Danielle K.,Chen, Xizhao,Bennett, Clay S.
, p. 3926 - 3934 (2017/04/11)
The use of a combination of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and β-pinene permits the removal of 2-naphthylmethyl (Nap) ether protecting groups on highly sensitive substrates. The reaction tolerates both acid and base sensitive protecting groups, and products are afforded in 68-96% yield. The utility of the method is demonstrated by the removal of the Nap protecting groups on highly sensitive 2,6-dideoxy-sugar disaccharides.
An Iron(III) Catalyst with Unusually Broad Substrate Scope in Regioselective Alkylation of Diols and Polyols
Ren, Bo,Ramstr?m, Olof,Zhang, Qiang,Ge, Jiantao,Dong, Hai
, p. 2481 - 2486 (2016/02/12)
In this study, [Fe(dibm)3] (dibm=diisobutyrylmethane) is shown to have unusually broad scope as a catalyst for the selective monoalkylation of a diverse set of 1,2- and 1,3-diol-containing structures. The mechanism is proposed to proceed via a cyclic dioxolane-type intermediate, formed between the iron(III) species and two adjacent hydroxyl groups. This approach represents the first transition-metal catalysts that are able to replace stoichiometric amounts of organotin reagents in regioselective alkylation. The reactions generally lead to very high regioselectivities and high yields, on par with, or better than, previous methods used for regioselective alkylation.
Aqueous Glycosylation of Unprotected Sucrose Employing Glycosyl Fluorides in the Presence of Calcium Ion and Trimethylamine
Pelletier, Guillaume,Zwicker, Aaron,Allen, C. Liana,Schepartz, Alanna,Miller, Scott J.
, p. 3175 - 3182 (2016/03/19)
We report a synthetic glycosylation reaction between sucrosyl acceptors and glycosyl fluoride donors to yield the derived trisaccharides. This reaction proceeds at room temperature in an aqueous solvent mixture. Calcium salts and a tertiary amine base promote the reaction with high site-selectivity for either the 3′-position or 1′-position of the fructofuranoside unit. Because nonenzymatic aqueous oligosaccharide syntheses are underdeveloped, mechanistic studies were carried out in order to identify the origin of the selectivity, which we hypothesized was related to the structure of the hydroxyl group array in sucrose. The solution conformation of various monodeoxysucrose analogs revealed the co-operative nature of the hydroxyl groups in mediating both this aqueous glycosyl bond-forming reaction and the site-selectivity at the same time.
