52389-39-6Relevant academic research and scientific papers
Synthesis of Aryl C-Glycosides via Iron-Catalyzed Cross Coupling of Halosugars: Stereoselective Anomeric Arylation of Glycosyl Radicals
Adak, Laksmikanta,Kawamura, Shintaro,Toma, Gabriel,Takenaka, Toshio,Isozaki, Katsuhiro,Takaya, Hikaru,Orita, Akihiro,Li, Ho C.,Shing, Tony K. M.,Nakamura, Masaharu
supporting information, p. 10693 - 10701 (2017/08/15)
We have developed a novel diastereoselective iron-catalyzed cross-coupling reaction of various glycosyl halides with aryl metal reagents for the efficient synthesis of aryl C-glycosides, which are of significant pharmaceutical interest due to their biological activities and resistance toward metabolic degradation. A variety of aryl, heteroaryl, and vinyl metal reagents can be cross-coupled with glycosyl halides in high yields in the presence of a well-defined iron complex, composed of iron(II) chloride and a bulky bisphosphine ligand, TMS-SciOPP. The chemoselective nature of the reaction allows the use of synthetically versatile acetyl-protected glycosyl donors and the incorporation of various functional groups on the aryl moieties, producing a diverse array of aryl C-glycosides, including Canagliflozin, an inhibitor of sodium-glucose cotransporter 2 (SGLT2), and a prevailing diabetes drug. The cross-coupling reaction proceeds via generation and stereoselective trapping of glycosyl radical intermediates, representing a rare example of highly stereoselective carbon-carbon bond formation based on iron catalysis. Radical probe experiments using 3,4,6-tri-O-acetyl-2-O-allyl-α-d-glucopyranosyl bromide (8) and 6-bromo-1-hexene (10) confirm the generation and intermediacy of the corresponding glycosyl radicals. Density functional theory (DFT) calculations reveal that the observed anomeric diastereoselectivity is attributable to the relative stability of the conformers of glycosyl radical intermediates. The present cross-coupling reaction demonstrates the potential of iron-catalyzed stereo- and chemoselective carbon-carbon bond formation in the synthesis of bioactive compounds of certain structural complexity.
Preparation and preliminary bioevaluation of a 99mTc(CO) 3-glucose derivative prepared by a click chemistry route
Fernandez, Soledad,Crocamo, Nancy,Incerti, Marcelo,Giglio, Javier,Scarone, Laura,Rey, Ana
experimental part, p. 274 - 280 (2012/09/22)
Development of a 99mTc-labelled glucose derivative as a single-photon emission computed tomography analogue to [18F]-2- fluoro-2-deoxy-D-glucose (FDG) is considered of great interest. Herein, we present the synthesis and preliminary bioevaluation of a 99mTc(CO) 3-glucose derivative. Derivatization of glucose at C2 was achieved using the so-called 'click chemistry', forming a histidine-like, 1,4-disubstituted triazole adequate as donor atom system for Tc(I)-tricarbonyl complexes. Synthesis of the intermediate azide derivative was achieved by conventional organic chemistry. Because of the efficiency and selectivity of this cycloaddition, labelling was performed in 'one pot', adding the tricarbonyl precursor fac-[99mTc(CO)3(H2O) 3]+ to the same vial where the click reaction has taken place without any further purification. A single product with radiochemical purity higher than 90% was obtained. It was stable for at least 4 h in reaction milieu and exhibited high hidrophilicity (log P of -1.2) and low binding to plasma proteins (5 ± 1%). Biodistribution in C57BL/6 mice bearing induced Lewis murine lung carcinoma is characterized by low blood and liver uptake and rapid urinary excretion. 99mTc complex showed moderate tumour uptake but significant retention until 2 h post-injection. Soft tissue clearance was fast leading to significantly higher uptake in tumour in comparison to muscle (p = 0.05) at all time points. Overall, biodistribution of our compound was very similar to that of [18F]-FDG. However, tumour uptake was significantly higher for [18F]-FDG, probably because of high hidrophilicity of our derivative that may hinder cell penetration. Similarity to biodistribution of FDG is a promising outcome, and modifications of the chelator and linker might improve biological results. Copyright
First synthesis of hunterioside, a novel disaccharide carrying monoterpenoid indole alkaloid, by assembly of three components, tryptamine, secologanin, and a newly-developed glucosyl donor
Ohmori, Osamu,Takayama, Hiromitsu,Aimi, Norio
, p. 5039 - 5042 (2007/10/03)
The novel structure of hunterioside, the first example of monoterpenoid indole alkaloids carrying a disaccharide, was confirmed by chemical synthesis starting from tryptamine, secologanin, and a newly-developed gulucosyl donor, which selectively gives α-g
The reaction of penta-O-benzoyl-D-glucopyranose with piperidine: Characterization of the products isolated and study of the reaction mechanism
Salinas, Amelia E.
, p. 34 - 46 (2007/10/03)
The reaction of penta-O-benzoyl-D-glucopyranose with piperidine gave N-(2,3,6-tri-O-benzoyl-β-D-glucopyranosyl)piperidine (44.1%), N-(2,4,6-tri-O-benzoyl-β-D-glucopyranosyl)piperidine (1.5%), N-benzoylpiperidine and piperidinium benzoate (approx 1 mol of each of these two products per mol of substrate). When several penta-O-benzoyl-D-glucopyranoses containing selectively 14C-labeled benzoyloxy groups were submitted to the same reaction, it was found that N-benzoylpiperidine is formed at the expense of benzoyloxy-C-1, piperidinium benzoate arises mainly from benzoyloxy-C-2, and the benzoyloxy groups originally attached to C-3, C-4, and C-6 remain in the major product of the reaction. These results demonstrate that the first compound produced in the reaction is N-(3,4,6-tri-O-benzoyl-β-D-glucopyranosyl)piperidine, which could not be isolated because it undergoes two consecutive benzoyl migrations: a migration from O-3 to O-2 to give the 2,4,6-tri-O-benzoate, followed by a migration from O-4 to O-3 to afford the 2,3,6-tri-O-benzoate. A mechanism to explain the formation of piperidinium benzoate from benzoyloxy-C-2 of penta-O-benzoyl-D-glucopyranose is proposed. Copyright (C) 1999 Elsevier Science Ltd.
