926625-06-1Relevant articles and documents
SUBSTITUTED, SATURATED AND UNSATURATED N-HETEROCYCLIC CARBOXAMIDES AND RELATED COMPOUNDS FOR THEIR USE IN THE TREATMENT OF MEDICAL DISORDERS
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, (2021/04/01)
The invention provides substituted, saturated and unsaturated N-heterocyclic carboxamides and related compounds, compositions containing such compounds, medical kits, and methods for using such compounds and compositions to treat medical disorders, e.g., cancer, lysosomal storage disorder, neurodegenerative disorder, inflammatory disorder, in a patient.
Synthesis and structural and photoswitchable properties of novel chiral host molecules: Axis chiral 2,2′-dihydroxy-1,1′-binaphthyl-appended stiff-stilbene
Shimasaki, Toshiaki,Kato, Shin-Ichiro,Ideta, Keiko,Goto, Kenta,Shinmyozu, Teruo
, p. 1073 - 1087 (2007/10/03)
(Chemical Equation Presented) Novel photoswitchable chiral hosts having an axis chiral 2,2′-dihydroxy-1,1′-binaphthyl (BINOL)-appended stiff-stilbene, trans-(R,R)- and -(S,S)-1, were synthesized by palladium-catalyzed Suzuki-Miyaura coupling and low-valence titanium-catalyzed McMurry coupling as key steps, and they were fully characterized by various NMR spectral techniques. The enantiomers of trans-1 showed almost complete mirror images in the CD spectra, where two split Cotton effects (exciton coupling) were observed in the β-transitions of the naphthyl chromophore at 222 and 235 nm, but no Cotton effect was observed in the stiff-stilbene chromophore at 365 nm. The structures of (R)-10 and trans-(R,R)-1 were confirmed by X-ray structural analysis. The optimized structure of cis-1 by MO calculations has a wide chiral cavity of 7-8 A in diameter, whereas trans-1 cannot form an intramolecular cavity based on the X-ray data. Irradiation of (R,R)-trans-1 with black light (λ = 365 nm) in CH3CN or benzene at 23°C led to the conversion to the corresponding cis-isomer, as was monitored by 1H NMR, UV - vis, and CD spectra. At the photostationary state, the cis-1/ trans-1 ratio was 86/14 in benzene or 75/25 in CH3CN. On the other hand, irradiation of the cis-1/trans-1 (75/25) mixture in CH3CN with an ultra-high-pressure Hg lamp at 23°C (λ = 410 nm) led to the photostationary state, where the cis-1/trans-1 ratio was estimated to be 9/91 on the basis of the 1H NMR spectra. The cis-trans and trans-cis interconversions could be repeated 10 times without decomposition of the C=C double bond. Thus, a new type of photoswitchable molecule has been developed, and trans-1 and cis-1 were quite durable under irradiation conditions. The guest binding properties of the BINOL moieties of trans- and cis-(R,R)-1 with F -, Cl-, and H2PO4- were examined by 1H NMR titration in CDCl3. Similar interaction with F- and Cl- was observed in trans-1 (host/guest = 1/1, Kassoc = (1.0 ± 0.13) × 103 for F - and (4.6 ± 0.72) × 102 M-1 for Cl-) and cis-1 (host/guest = 1/1, Kassoc = (1.0 ± 0.13) × 103 for F- and (5.9 ± 0.69) × 10 M-1 for Cl-), but H2PO4 - interacted differently: the cis-isomer formed the 1/1 complex (Kassoc = (9.38 ± 2.67) × 10 M-1), whereas multistep equilibrium was expected for the trans-isomer.