6411-34-3Relevant academic research and scientific papers
Protein Glycosylation through Sulfur Fluoride Exchange (SuFEx) Chemistry: The Key Role of a Fluorosulfate Thiolactoside
Marra, Alberto,Dong, Jiajia,Ma, Tiancheng,Giuntini, Stefano,Crescenzo, Elisa,Cerofolini, Linda,Martinucci, Marco,Luchinat, Claudio,Fragai, Marco,Nativi, Cristina,Dondoni, Alessandro
, p. 18981 - 18987 (2018)
Protein glycosylation is the most complex post-translational modification process. More than 50 % of human cells proteins are glycosylated, whereas bacteria such as E. coli do not have this modification machinery. Indeed, the carbohydrate residues in natural proteins affect their folding, immunogenicity, and stability toward proteases, besides controlling biological properties and activities. It is therefore important to introduce such structural modification in bioengineered proteins lacking the presence of carbohydrate residues. This is not trivial as it requires reagents and conditions compatible with the protein's stability and reactivity. This work reports on the introduction of lactose moieties in two natural proteins, namely ubiquitin (Ub) and l-asparaginase II (ANSII). The synthetic route employed is based on the sulfur(VI) fluoride exchange (SuFEx) coupling of a lactose tethered arylfluorosulfate (Lact-Ar-OSO2F) with the ?-NH2 group of lysine residues of the proteins. This metal-free click SuFEx reaction relies on the properties of the fluorosulfate employed, which is easily prepared in multigram scale from available precursors and reacts chemoselectively with the ?-NH2 group of lysine residues under mild conditions. Thus, iterative couplings of Lact-Ar-OSO2F to Ub and ANSII, afforded multiple glycosylations of these proteins so that up to three and four Lact-Ar-OSO2 groups were introduced in Ub and ANSII, respectively, via the formation of a sulfamoyl (OSO2-NH) linkage.
Chiral trialkanolamine-based hemicryptophanes: Synthesis and oxovanadium complex
Gautier, Arnaud,Mulatier, Jean-Christophe,Crassous, Jeanne,Dutasta, Jean-Pierre
, p. 1207 - 1210 (2005)
(Chemical Equation Presented) A novel class of chiral hemicryptophane hosts has been synthesized in diastereoisomerically pure form, namely, M-(R,R,R)-1a/P-(S,S,S)-1a and M-(S,S,S)-1b/P-(R,R,R)-1b. The C 3-symmetrical precursor 9 was prepared, using either (R)- or (S)-glycidyl nosylate, repectively, as the chiral pool reactant and subsequently cyclized (trimerized) in the presence of Sc(OTf)3. The four stereoisomers were fully characterized and displayed two pairs of mirror-image CD spectra, which were used to determine their absolute configuration. The formation of the oxovanadium-(V) complex of hemicryptophane 1a is also reported.
Nickel Hydride Catalyzed Cleavage of Allyl Ethers Induced by Isomerization
Kathe, Prasad M.,Berkefeld, Andreas,Fleischer, Ivana
supporting information, p. 1629 - 1632 (2021/02/09)
This report discloses the deallylation of O - and N -allyl functional groups by using a combination of a Ni-H precatalyst and excess Bronsted acid. Key steps are the isomerization of the O - or N -allyl group through Ni-catalyzed double-bond migration followed by Bronsted acid induced O/N-C bond hydrolysis. A variety of functional groups are tolerated in this protocol, highlighting its synthetic value.
Nickel-catalyzed deallylation of aryl allyl ethers with hydrosilanes
Ding, Guangni,Fan, Sijie,Wang, Jingyang,Wang, Yu,Wu, Xiaoyu,Xie, Xiaomin,Yang, Liqun,Zhang, Zhaoguo
supporting information, (2021/09/28)
An efficient and mild catalytic deallylation method of aryl allyl ethers is developed, with commercially available Ni(COD)2 as catalyst precursor, simple substituted bipyridine as ligand and air-stable hydrosilanes. The process is compatible with a variety of functional groups and the desired phenol products can be obtained with excellent yields and selectivity. Besides, by detection or isolation of key intermediates, mechanism studies confirm that the deallylation undergoes η3-allylnickel intermediate pathway.
Enantioselective Synthesis of 3-Fluorochromanes via Iodine(I)/Iodine(III) Catalysis
Daniliuc, Constantin G.,Gilmour, Ryan,Neufeld, Jessica,Sarie, Jér?me C.,Thiehoff, Christian
supporting information, p. 15069 - 15075 (2020/06/17)
The chromane nucleus is common to a plenum of bioactive small molecules where it is frequently oxidized at position 3. Motivated by the importance of this position in conferring efficacy, and the prominence of bioisosterism in drug discovery, an iodine(I)/iodine(III) catalysis strategy to access enantioenriched 3-fluorochromanes is disclosed (up to 7:93 e.r.). In situ generation of ArIF2 enables the direct fluorocyclization of allyl phenyl ethers to generate novel scaffolds that manifest the stereoelectronic gauche effect. Mechanistic interrogation using deuterated probes confirms a stereospecific process consistent with a type IIinv pathway.
CELL CYCLE PROGRESSION INHIBITOR
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Paragraph 0086, (2019/09/18)
The present invention provides a cell cycle progression inhibitor, a cytostatic agent, and an anticancer agent. The cell cycle progression inhibitor, the cytostatic agent, and the anticancer agent each contains a Hes1 protein-PHB2 protein binding enhancer.
Direct Aryloxylation/Alkyloxylation of Dialkyl Phosphonates for the Synthesis of Mixed Phosphonates
Huang, Hai,Denne, Johanna,Yang, Chou-Hsun,Wang, Haobin,Kang, Jun Yong
supporting information, p. 6624 - 6628 (2018/05/14)
A strategy for the direct functionalization strategy of inertial dialkyl phosphonates with hydroxy compounds to afford diverse mixed phosphonates with good yields and functional-group tolerance has been developed. Mechanistic investigations involving both NMR studies and DFT studies suggest that an unprecedented highly reactive PV species (phosphoryl pyridin-1-ium salt), a key intermediate for this new synthetic transformation, is generated in situ from dialkyl phosphonate in the presence of Tf2O/pyridine.
AMINATION AND HYDROXYLATION OF ARYLMETAL COMPOUNDS
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Paragraph 0098; 0226; 0243, (2018/03/25)
In one aspect, the present disclosure provides methods of preparing a primary or secondary amine and hydroxylated aromatic compounds. In some embodiments, the aromatic compound may be unsubstituted, substituted, or contain one or more heteroatoms within the rings of the aromatic compound. The methods described herein may be carried out without the need for transition metal catalysts or harsh reaction conditions.
Combining Orthogonal Chain-End Deprotections and Thiol–Maleimide Michael Coupling: Engineering Discrete Oligomers by an Iterative Growth Strategy
Huang, Zhihao,Zhao, Junfei,Wang, Zimu,Meng, Fanying,Ding, Kunshan,Pan, Xiangqiang,Zhou, Nianchen,Li, Xiaopeng,Zhang, Zhengbiao,Zhu, Xiulin
supporting information, p. 13612 - 13617 (2017/10/24)
Orthogonal maleimide and thiol deprotections were combined with thiol–maleimide coupling to synthesize discrete oligomers/macromolecules on a gram scale with molecular weights up to 27.4 kDa (128mer, 7.9 g) using an iterative exponential growth strategy with a degree of polymerization (DP) of 2n?1. Using the same chemistry, a “readable” sequence-defined oligomer and a discrete cyclic topology were also created. Furthermore, uniform dendrons were fabricated using sequential growth (DP=2n?1) or double exponential dendrimer growth approaches (DP=2 22n ?1) with significantly accelerated growth rates. A versatile, efficient, and metal-free method for construction of discrete oligomers with tailored structures and a high growth rate would greatly facilitate research into the structure–property relationships of sophisticated polymeric materials.
Rapid heteroatom transfer to arylmetals utilizing multifunctional reagent scaffolds
Gao, Hongyin,Zhou, Zhe,Kwon, Doo-Hyun,Coombs, James,Jones, Steven,Behnke, Nicole Erin,Ess, Daniel H.,Kürti, László
, p. 681 - 688 (2017/06/30)
Arylmetals are highly valuable carbon nucleophiles that are readily and inexpensively prepared from aryl halides or arenes and widely used on both laboratory and industrial scales to react directly with a wide range of electrophiles. Although C-C bond formation has been a staple of organic synthesis, the direct transfer of primary amino (-NH2) and hydroxyl (-OH) groups to arylmetals in a scalable and environmentally friendly fashion remains a formidable synthetic challenge because of the absence of suitable heteroatom-transfer reagents. Here, we demonstrate the use of bench-stable N-H and N-alkyl oxaziridines derived from readily available terpenoid scaffolds as efficient multifunctional reagents for the direct primary amination and hydroxylation of structurally diverse aryl- and heteroarylmetals. This practical and scalable method provides one-step synthetic access to primary anilines and phenols at low temperature and avoids the use of transition-metal catalysts, ligands and additives, nitrogen-protecting groups, excess reagents and harsh workup conditions.
