35761-91-2Relevant academic research and scientific papers
Diastereoselective access to polyoxygenated polycyclic spirolactones through a rhodium-catalyzed [3+2] cycloaddition reaction: Experimental and theoretical studies
Rodier, Fabien,Rajzmann, Michel,Parrain, Jean-Luc,Chouraqui, Ga?lle,Commeiras, Laurent
, p. 2467 - 2477 (2013)
The synthetic utility of γ-alkylidenebutenolides is demonstrated as highly competent dipolarophile partners in both intra- and intermolecular rhodium(II)-catalyzed 1,3-dipolar cycloaddition reactions. The strength of this approach lies in the formation of spiro[6,4]lactone moieties with the concomitant construction of quaternary spiro stereocenters. Typically, the construction of spirolactones involves an esterification step, which has often been reported as a "biosynthetic pathway", and often occurs either as or near to the final step of a total synthesis. Furthermore, a convergent and versatile route is reported for the formation of the (5,7) skeleton of molecules that were isolated from the Schisandra genus. Computational studies were performed to provide an overall picture of the mechanism of the intermolecular [3+2] cycloaddition between 2-diazo-1,3-ketoester and protoanemonin and to rationalize the empirical observations. In particular, we have demonstrated for the first time that the rhodium center plays an important role during the cyclization step itself and reacts with the dipolarophile as a complex with the ylide. A rapid regio- and diastereoselective access to functionalized rigid polycyclic systems that contain a spiro[6.4] moiety through a Rh-catalyzed [3+2] cycloaddition is described (see scheme). A theoretical treatment rationalized the empirical observations. Copyright
INTRACELLULAR DELIVERY VEHICLE
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, (2020/08/13)
PROBLEM TO BE SOLVED: To provide a vehicle which can easily deliver a desired component or compound into a cell without preventing cell proliferation. SOLUTION: A intracellular delivery vehicle has its surface covered with positive electric charge. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
Total synthesis of the actinoallolides and a designed photoaffinity probe for target identification
Anketell, Matthew J.,Paterson, Ian,Sharrock, Theodore M.
supporting information, p. 8109 - 8118 (2020/11/03)
The actinoallolides are a family of polyketide natural products isolated from the bacterium Actinoallomurus fulvus. They show potent biological activity against trypanosomes, the causative agents of the neglected tropical diseases human African trypanosomiasis (sleeping sickness) and Chagas disease, while exhibiting no cytotoxicity against human cell lines. Herein, we give a full account of our strategy evolution towards the synthesis of this structurally unique class of 12-membered macrolides, which culminated in the first total synthesis of (+)-actinoallolide A in 20 steps and 8% overall yield. Subsequent late-stage diversification then provided ready access to the congeneric (+)-actinoallolides B-E. Enabled by this flexible and efficient endgame sequence, we also describe the design and synthesis of a photoaffinity probe based on actinoallolide A to investigate its biological mode of action. This will allow ongoing labelling studies to identify their protein binding target(s). This journal is
INTRACELLULAR DELIVERY VEHICLE
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, (2019/05/18)
An intracellular delivery vehicle of which surface is covered by a positive charge, an intracellular delivery complex in which a component or compound desired is loaded in the intracellular delivery vehicle, a temperature-sensitive probe comprising the intracellular delivery complex, and a method for measuring the intracellular temperature by the temperature-sensitive probe are disclosed. The intracellular delivery vehicle is useful on account of its capability of easily delivering the component or compound desired inside the cell without inhibiting cell proliferation.
A Cell-Targeted Non-Cytotoxic Fluorescent Nanogel Thermometer Created with an Imidazolium-Containing Cationic Radical Initiator
Uchiyama, Seiichi,Tsuji, Toshikazu,Kawamoto, Kyoko,Okano, Kentaro,Fukatsu, Eiko,Noro, Takahiro,Ikado, Kumiko,Yamada, Sayuri,Shibata, Yuka,Hayashi, Teruyuki,Inada, Noriko,Kato, Masaru,Koizumi, Hideki,Tokuyama, Hidetoshi
supporting information, p. 5413 - 5417 (2018/04/09)
A cationic fluorescent nanogel thermometer based on thermo-responsive N-isopropylacrylamide and environment-sensitive benzothiadiazole was developed with a new azo compound bearing imidazolium rings as the first cationic radical initiator. This cationic fluorescent nanogel thermometer showed an excellent ability to enter live mammalian cells in a short incubation period (10 min), a high sensitivity to temperature variations in live cells (temperature resolution of 0.02–0.84 °C in the range 20–40 °C), and remarkable non-cytotoxicity, which permitted ordinary cell proliferation and even differentiation of primary cultured cells.
Identifying Glyceraldehyde 3-Phosphate Dehydrogenase as a Cyclic Adenosine Diphosphoribose Binding Protein by Photoaffinity Protein-Ligand Labeling Approach
Zhang, Kehui,Sun, Wei,Huang, Linong,Zhu, Kaiyuan,Pei, Fen,Zhu, Longchao,Wang, Qian,Lu, Yingying,Zhang, Hongmin,Jin, Hongwei,Zhang, Li-He,Zhang, Liangren,Yue, Jianbo
, p. 156 - 170 (2017/05/16)
Cyclic adenosine diphosphoribose (cADPR), an endogenous nucleotide derived from nicotinamide adenine dinucleotide (NAD+), mobilizes Ca2+ release from endoplasmic reticulum (ER) via ryanodine receptors (RyRs), yet the bridging protein(s) between cADPR and RyRs remain(s) unknown. Here we synthesized a novel photoaffinity labeling (PAL) cADPR agonist, PAL-cIDPRE, and subsequently applied it to purify its binding proteins in human Jurkat T cells. We identified glyceraldehyde 3-phosphate dehydrogenase (GAPDH) as one of the cADPR binding protein(s), characterized the binding affinity between cADPR and GAPDH in vitro by surface plasmon resonance (SPR) assay, and mapped cADPR's binding sites in GAPDH. We further demonstrated that cADPR induces the transient interaction between GAPDH and RyRs in vivo and that GAPDH knockdown abolished cADPR-induced Ca2+ release. However, GAPDH did not catalyze cADPR into any other known or novel compound(s). In summary, our data clearly indicate that GAPDH is the long-sought-after cADPR binding protein and is required for cADPR-mediated Ca2+ mobilization from ER via RyRs.
Synthesis and evaluation of a tag-free photoactive phospho-ceramide analogue-1 (PCERA-1) probe to study immunomodulation in macrophages
Dandela, Rambabu,Mashiach, Roi,Adepu, Raju,Gregor, Rachel,Athamna, Muhammad,Zecharia, Efrat,Ernst, Orna,Zor, Tsaffrir,Meijler, Michael M.
supporting information, p. 3842 - 3845 (2017/04/04)
Phospho-ceramide analogue-1 (PCERA-1), a synthetic analogue of ceramide-1-phosphate (C1P), has been previously shown to act as a potent modulator of macrophage activity and inflammation. We have developed an efficient synthesis of PCERA-1 from readily available starting materials, and designed and prepared derivatives of this analogue, including a photoaffinity probe to tag and identify putative proteins that bind PCERA-1.
Construction of Hexahydrophenanthrenes By Rhodium(I)-Catalyzed Cycloisomerization of Benzylallene-Substituted Internal Alkynes through C?H Activation
Kawaguchi, Yasuaki,Yasuda, Shigeo,Mukai, Chisato
supporting information, p. 10473 - 10477 (2016/08/24)
The treatment of benzylallene-substituted internal alkynes with [RhCl(CO)2]2effects a novel cycloisomerization by C(sp2)?H bond activation to produce hexahydrophenanthrene derivatives. The reaction likely proceeds through consecutive formation of a rhodabicyclo[4.3.0] intermediate, σ-bond metathesis between the C(sp2)?H bond on the benzene ring and the C(sp2)?RhIIIbond, and isomerization between three σ-, π-, and σ-allylrhodium(III) species, which was proposed based on experiments with deuterated substrates.
Dendritic fluoroalcohols as catalysts for alkene epoxidation with hydrogen peroxide
Berkessel, Albrecht,Kraemer, Jan,Mummy, Florian,Neudoerfl, Joerg-M.,Haag, Rainer
, p. 739 - 743 (2013/02/23)
Cooperativity is the key for mild catalytic epoxidation: The immobilization of fluoroalcohols on dendritic polyglycerol (by "click chemistry") provides organocatalysts that can form multiple hydrogen bonds. The epoxidation of alkenes with aqueous hydrogen peroxide proceeds efficiently in the presence of dendritic fluoroalcohol catalysts. The supported catalysts can be separated by membrane filtration and reused. Copyright
The difference in reactivity of (-)-mono and dimenthyl vs. diethyl alkylphosphonates in the α-lithiation reaction: Carbanionic synthesis of unknown (-)-dimenthyl 1-iodoalkylphosphonates and their first use in the radical iodine atom transfer addition (I-A
Ba?czewski, Piotr,Szadowiak, Aldona,Bodzioch, Agnieszka,Bia?as, Tomasz,Wieczorek, Wanda M.,Szyrej, Ma?gorzata
, p. 997 - 1009 (2007/10/03)
Unknown (-)-dimenthyl and ethyl (-)-menthyl 1-iodoethylphosphonates were synthesized via 1-lithio derivatives in 85-87% yields. Starting (-)-dimenthyl alkylphosphonates (R = Me, Et, i-Pr) were obtained in the Michaelis-Becker reaction (75-81% yields) and/
