927-73-1Relevant articles and documents
Scalable Total Synthesis, IP3R Inhibitory Activity of Desmethylxestospongin B, and Effect on Mitochondrial Function and Cancer Cell Survival
Podunavac, Ma?a,Mailyan, Artur K.,Jackson, Jeffrey J.,Lovy, Alenka,Farias, Paula,Huerta, Hernan,Molgó, Jordi,Cardenas, Cesar,Zakarian, Armen
supporting information, p. 11278 - 11282 (2021/04/19)
The scalable synthesis of the oxaquinolizidine marine natural product desmethylxestospongin B is based on the early application of Ireland–Claisen rearrangement, macrolactamization, and a late-stage installation of the oxaquinolizidine units by lactam reduction. The synthesis serves as the source of material to investigate calcium signaling and its effect on mitochondrial metabolism in various cell types, including cancer cells.
2-AZABICYCLO[3.1.1] DERIVATIVES AS ANTAGONISTS OF THE OREXIN-1 AND OREXIN-2 RECEPTORS
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Page/Page column 44, (2019/05/15)
There is provided a compound of formula I, wherein L1, R1, R2, R5, X, A and B have meanings given in the description, and pharmaceutically acceptable salts, solvates and prodrugs thereof, which compounds are useful as antagonists of the orexin-1 and orexin-2 receptors or as selective antagonists of the orexin-1 receptor, and thus, in particular, in the treatment or prevention of inter alia substance dependence, addiction, anxiety disorders, panic disorders, binge eating, compulsive disorders, impulse control disorders, cognitive impairment and Alzheimer's disease.
Total synthesis of carolacton, a highly potent biofilm inhibitor
Schmidt, Thomas,Kirschning, Andreas
supporting information; experimental part, p. 1063 - 1066 (2012/03/11)
Metals are the key players in the synthesis of caralacton, a strong inhibitor of bacterial biofilms. The total synthesis is based on several metal-mediated key transformations such as the Ley and the Duthaler-Hafner aldol reactions, the Marshall reaction and Breit's substitution, as well as the Nozaki-Hiyama-Kishi and Negishi-Fu C-C coupling reactions. Copyright
Skeletal and stereochemical diversification of tricyclic frameworks inspired by Ca2+-ATPaSe inhibitors, artemisinin and transtaganolide D
Oguri, Hiroki,Yamagishi, Yutaka,Hiruma, Takahisa,Oikawa, Hideaki
supporting information; experimental part, p. 601 - 604 (2009/09/25)
(Chemical Equation Presented) Inspired by the common skeletal motifs of Ca2+-ATPases inhibitors involving artemisinin and transtaganolide D, small molecule collections with the three-dimensional structural diversity of tricyclic systems were designed and expeditiously synthesized (4-5 steps). A synthetic strategy featuring stereochemical diversification of ring-junctions and control of cyclizatlon modes was devised to access varied molecular architectures in a systematic fashion.
Rearrangement, nucleophilic substitution, and halogen switch reactions of alkyl halides over NaY zeolite: Formation of the bicyclobutonium cation inside the zeolite cavity
Franco, Marcelo,Rosenbach Jr., Nilton,Ferreira, Glaucio B.,Guerra, Antonio C. O.,Kover, W. Bruce,Turci, Cassia C.,Mota, Claudio J. A.
, p. 1592 - 1600 (2008/09/18)
Rearrangement and nucleophilic substitution of cyclopropylcarbinyl bromide over NaY and NaY impregnated with NaCl was observed at room temperature. The first-order kinetics are consistent with ionization to the bicyclobutonium cation, followed by internal return of the bromide anion or nucleophilic attack by impregnated NaCl to form cyclopropylcarbinyl, cyclobutyl, and allylcarbinyl chlorides. The product distribution analysis revealed that neither a purely kinetic distribution, similar to what is found in solution, nor the thermodynamic ratio, which favors the allylcarbinyl halide, was observed. Calculations showed that bicyclobutonium and cyclopropylcarbinyl carbocations are minimal over the zeolite structure, and stabilized by hydrogen bonding with the framework structure. A new process of nucleophilic substitution is reported, namely halogen switch, involving alkyl chlorides and bromides of different structures. The reaction occurs inside the zeolite pores, due to the confinement effects and is an additional proof of carbocation formation on zeolites. The results support the idea that zeolites act as solid solvents, permitting ionization and solvation of ionic species.
Rearrangements concerted with fragmentation of cyclopropylmethoxychlorocarbene and cyclobutoxychlorocarbene in hydrocarbon solvents and Ar matrices
Moss, Robert A.,Sauers, Ronald R.,Zheng, Fengmei,Fu, Xiaolin,Bally, Thomas,Maltsev, Alexander
, p. 8466 - 8476 (2007/10/03)
Fragmentations of cyclopropylmethoxychlorocarbene (6) and cyclobutoxychlorocarbene (10) lead to rearrangments that afford mixtures of cyclopropylmethyl chloride (7), cyclobutyl chloride (8), and 3-butenyl chloride (9). Isotopic substitution studies show that these rearrangments are accompanied by partial exchange of the methylene groups within 6 and 10. Surprisingly, these processes that are typical of carbocations persist in hydrocarbon solvents such as pentane and cyclohexane-d12. Quantum chemical calculations reveal that the cis-conformers of the incipient oxychlorocarbenes C 4H7OCCl decay to C4H7Cl + CO via transient hydrogen bonded C4H7 σ+...Clσ- complexes which possess significant ion pair character, even in the gas phase or in nonpolar solvents. In contrast to benzyloxychlorocarbene, no free radicals are formed upon generation or photolysis of 6 or 10 in Ar matrixes, although acid chlorides (the recombination products of these radical pairs) are observed. The IR spectra obtained in these experiments show the presence of several conformers of the two C4H7OCCl.
Fragmentation of alkoxychlorocarbenes in the gas phase
Blake, Michael E,Jones Jr., Maitland,Zheng, Fengmei,Moss, Robert A
, p. 3069 - 3071 (2007/10/03)
In contrast to photolysis or thermal decomposition in solution, which is dominated by ionic reactions, flash vacuum pyrolysis of alkylchlorodiazirines in the gas phase generates radicals. The cyclopropylcarbinyl system is re-examined and the l-norbornylca
Fragmentation of cyclobutoxychlorocarbene: The cyclopropylcarbinyl/cyclobutyl cations revisited
Moss, Robert A.,Zheng, Fengmei,Johnson, Lauren A.,Sauers, Ronald R.
, p. 400 - 406 (2007/10/03)
Fragmentations of cyclobutoxychlorocarbene (13, kfrag= 7.1 × 105 s-1) and cyclopropylmethoxychlorocarbene (14, kfrag = 7.6 × 105 s-1) in MeCN proceed to tight and distinct [R+ OC Cl-] ion pairs, which collapse to different distributions of cyclopropylcarbinyl, cyclobutyl and allylcarbinyl chlorides. B3LYP/6-31G* calculations support these conclusions, affording computed fragmentation activation energies of 6.4 (13) and 3.0 (14) kcal mol-1.
Absolute rate constants for abstraction of chlorine from three chlorinating agents by alkyl radicals
Tanko, James M.,Blackert, Joseph F.
, p. 1775 - 1780 (2007/10/03)
Using the cyclopropylcarbinyl -> homoallyl free radical clock, absolute rate constants for the abstraction of chlorine from molecular chlorine (Cl2), tert-butyl hypochlorite (ButOCl) and N-chloro-3,3-dimethylglutarimide (NCG) have been determined (kCl2=3.0*1010, kButOCl=2.6*109 and kNCG=3.6*107, all in 1 mol-1s-1).
FRAGMENTATION OF CYCLOPROPYLMETHOXYCHLOROCARBENE: FORMATION OF CYCLOPROPYLCARBINYL/CHLORIDE ION PAIRS
Moss, Robert A.,Ho, Guo Jie,Wilk, Bogdan K.
, p. 2473 - 2476 (2007/10/02)
The decomposition of cyclopropylmethyloxychlorodiazirine in MeCN proceeds via N2 and CO loss, mainly to tight cyclopropylcarbinyl cation-chloride anion pairs that collapse to C4 chlorides with substantial skeletal and label retention; the ion pairs can be intercepted by ethanol with less skeletal retention.
