539-87-7Relevant academic research and scientific papers
Conformations of Oxocane
Meyer, Walter L.,Taylor, Patterson W.,Reed, Scott A.,Leister, Marvin C.,Schneider, Hans-Joerg,et al.
, p. 291 - 298 (1992)
Conformational analysis of oxocane (oxacyclooctane) has been examined by molecular mechanics (MM2), variable-temperature 13C NMR, and lanthanide-induced shift (LIS) 1H and 13C NMR.MM2 calculations find the BC-3 conformer and its enantiomer BC-7 to be favored, with the four next best forms and their energies relative to BC-3-being BC-1 (1.1 kcal/mol), TBC-1(1.1), BC-4(1.5), and TCC-1(1.6).Barriers to pseudorotational interconversion of BC-3 and BC-7 are calculated to be 5.0 kcal/mol through BC-5 and 6.7 kcal/mol through BC-1.The former would allow fast BC-3/BC-7 equilibration even at -170 deg C, which would leave reported low-temperature 1H NMR spectra compatible with a BC-3 structure as well as BC-1.Calculated barriers for BC ring inversion and interconversion of the BC family with the crown family (TCC-1) are 8.2 and 8.5 kcal/mol, respectively.A new two-step synthesis of oxocane and its 2,2,7,7-d4 analogue is reported, the latter allowing unequivocal assignment of chemical shifts. 13C NMR spectra of oxocane between 138 and 290 K show BC-family/crown-family inter-conversion in the vicinity of 215 K (ΔG(excit.) = 10.0 +/- 0.3 kcal/mol), with the crown family comprising 4percent of the equilibrium at 174 K (ΔG0 = 1.1 +/- 0.1 kcal/mol).The 1H and 13C LIS induced by Yb(fod)3 on oxocane agree well with BC-3 and BC-7 being the predominant conformers at room temperature but do not acceptably fit a BC-1 structure.Thus, all available data from calculation and experiment are in accord with BC-3 being the favored conformation of oxocane.
Microwave-assisted polymer chemistry: Heck-reaction, transesterification, Baeyer-Villiger oxidation, oxazoline polymerization, acrylamides, and porous materials
Koopmans, Carsten,Iannelli, Mauro,Kerep, Patrick,Klink, Michael,Schmitz, Sarah,Sinnwell, Sebastian,Ritter, Helmut
, p. 4709 - 4714 (2006)
Several questions are still open concerning the different effects of microwave (MW) irradiation in organic and macromolecular chemistry. Analyzing experimental results on a relatively broad investigation area, we came to elucidate three main effects of microwave irradiation: efficient non-contact heating, an accelerating effect, and what we term a special effect. In this paper, we report the first MW-assisted synthesis of poly(2,5-dibutoxy-1,4-phenylenevinylene) via Heck-polycondensation as an example for efficient heating. The facile synthesis of the higher lactones 1-oxa-2-oxocyclooctanone and 1-oxa-2-oxocyclononanone via Baeyer-Villiger reaction offers indeed an example for the MW-accelerating effect. A survey of our recent work is also given to explain the effects more in detail and to provide examples of the special MW effect.
PEGylated Poly-HDACi: A Designer Polyprodrug from Optimized Drug Units**
Han, Jinghua,Huang, Qingqing,Kang, Yanke,Li, Jing,Luo, Zihan,Lv, Wenhui,Meng, Li,Shen, Jie,Wang, Da-Yuan,Wang, Peng George,Wang, Qiuyu,Wang, Yajie,Wang, Yanming
supporting information, (2021/12/22)
We designed, synthesized, and characterized a tri-block copolymer. Its hydrophobic part, a chain of histone deacetylase inhibitor (HDACi) prodrug, was symmetrically flanked by two identical PEG blocks, whereas the built-in HDACi was a linear molecule, terminated with a thiol at one end, and a hydroxyl group at the other. Such a feature facilitated end-to-end linkage of prodrugs through alternatively aligned disulfides and carbonates. The disulfides served dual roles: redox sensors of smart nanomedicine, and warheads of masked HDACi drugs. This approach, carefully designed to benefit both control-release and efficacy, is conceptually novel for optimizing drug units in nanomedicine. Micelles from this designer polyprodrug released only PEG, CO2 and HDACi, and synergized with DOX against HCT116 cells, demonstrating its widespread potential in combination therapy. Our work highlights, for the first time, the unique advantage of thiol-based drug molecules in nanomedicine design.
Green Oxidation of Ketones to Lactones with Oxone in Water
Bertolini, Valentina,Appiani, Rebecca,Pallavicini, Marco,Bolchi, Cristiano
, p. 15712 - 15716 (2021/11/01)
Cyclic ketones were quickly and quantitatively converted to 5-, 6-, and 7-membered lactones, very important synthons, by treatment with Oxone, a cheap, stable, and nonpollutant oxidizing reagent, in 1 M NaH2PO4/Na2HPO4 water solution (pH 7). Under such simple and green conditions, no hydroxyacid was formed, thus making the adoption of more complex and non-eco-friendly procedures previously developed to avoid lactone hydrolysis unnecessary. With some changes, the method was successfully applied also to water-insoluble ketones such as adamantanone, acetophenone, 2-indanone, and the challenging cycloheptanone.
A Polyketide Cyclase That Forms Medium-Ring Lactones
Gao, De-Wei,Jamieson, Cooper S.,Wang, Gaoqian,Yan, Yan,Zhou, Jiahai,Houk,Tang, Yi
, p. 80 - 84 (2021/01/13)
Medium-ring lactones are synthetically challenging due to unfavorable energetics involved in cyclization. We have discovered a thioesterase enzyme DcsB, from the decarestrictine C1 (1) biosynthetic pathway, that efficiently performs medium-ring lactonizations. DcsB shows broad substrate promiscuity toward linear substrates that vary in lengths and substituents, and is a potential biocatalyst for lactonization. X-ray crystal structure and computational analyses provide insights into the molecular basis of catalysis.
LIPID PRODRUGS OF BTK INHIBITORS AND USES THEREOF
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Paragraph 00405; 00560; 00561, (2020/09/12)
The present invention provides lymphatic system-directing lipid prodrugs, pharmaceutical compositions thereof, methods of producing such prodrugs and compositions, and methods of improving the bioavailability or other properties of a therapeutic agent that comprises part of the lipid prodrug. The present invention also provides methods of treating a disease, disorder, or condition such as those disclosed herein, comprising administering to a patient in need thereof a disclosed lipid prodrug or a pharmaceutical composition thereof.
LIPID PRODRUGS OF GLUCOCORTICOIDS AND USES THEREOF
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Paragraph 00544; 00545, (2020/09/12)
The present invention provides lymphatic system-directing lipid prodrugs, pharmaceutical compositions thereof, methods of producing such prodrugs and compositions, and methods of improving the bioavailability or other properties of a therapeutic agent that comprises part of the lipid prodrug. The present invention also provides methods of treating a disease, disorder, or condition such as those disclosed herein, comprising administering to a patient in need thereof a disclosed lipid prodrug or a pharmaceutical composition thereof.
Stereoselective synthesis of MaR2n-3 DPA
S?nderskov, Jeanne,Tungen, J?rn E.,Palmas, Francesco,Dalli, Jesmond,Serhan, Charles N.,Stenstr?m, Yngve,Vidar Hansen, Trond
supporting information, (2019/12/24)
The first total synthesis of the n-3 docosapentaenoic derived oxygenated product MaR2n-3 DPA has been achieved. The 13R and 14S stereogenic centers were introduced using 2-deoxy-D-ribose in a chiral pool strategy. The geometry of the Z,E,E-triene moiety was prepared using highly E-selective Wittig- and Takai-olefination reactions as well as the Z-stereoselective Lindlar reduction. LC/MS-MS data of synthetic MaR2n-3 DPA matched data for the biosynthetic formed product that enabled the configurational assignment of this oxygenated natural product to be (7Z,9E,11E,13R,14S,16Z,19Z)-13,14-dihydroxydocosa-7,9,11,16,19-pentaenoic acid.
INHIBITORS OF HISTONE DEACETYLASE USEFUL FOR THE TREATMENT OR PREVENTION OF HIV INFECTION
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Page/Page column 39, (2020/02/23)
The present invention relates to Compounds of Formula (I): Formula (I) and pharmaceutically acceptable salts or prodrug thereof, wherein R1, R2, R3, Ra, Rb, A and B are as defined herein. The present invention also relates to compositions comprising at least one compound of Formula (I), and methods of using the compounds of Formula (I) for treating or preventing HIV infection in a subject.
Photoenzymatic Generation of Unstabilized Alkyl Radicals: An Asymmetric Reductive Cyclization
Clayman, Phillip D.,Hyster, Todd K.
supporting information, p. 15673 - 15677 (2020/10/18)
Flavin-dependent "ene"-reductases can generate stabilized alkyl radicals when irradiated with visible light; however, they are not known to form unstabilized radicals. Here, we report an enantioselective radical cyclization using alkyl iodides as precursors to unstabilized nucleophilic radicals. Evidence suggests this species is accessed by photoexcitation of a charge-transfer complex that forms between flavin and substrate within the protein active site. Stereoselective delivery of a hydrogen atom from the flavin semiquinone to the prochiral radical formed after cyclization provides high levels of enantioselectivity across a variety of substrates. Overall, this transformation demonstrates that photoenzymatic catalysis can address long-standing selectivity challenges in the radical literature.
