579-74-8Relevant articles and documents
-OH-Induced shift from carbon to oxygen acidity in the side-chain deprotonation of 2-, 3- and 4-methoxybenzyl alcohol radical cations in aqueous solution: Results from pulse radiolysis and DFT calculations
Baciocchi, Enrico,Bietti, Massimo,Ercolani, Gianfranco,Steenken, Steen
, p. 613 - 618 (2003)
DFT calculations have been carried out for 2-, 3- and 4-methoxybenzyl alcohol radical cations (1·+, 3·+ and 4·+, respectively) and the α-methyl derivatives 2·+ and 5·+ using the UB3LYP/6-31G(d) method. The theoretical results have been compared with the experimental rate constants for deprotonation of 1·+-5·+ under acidic and basic conditions. In acidic solution, the decay of 1·+-5·+ proceeds by cleavage of the C-H bond, while in the presence of -OH all the radical cations undergo deprotonation from the α-OH group. This pH-dependent change in mechanism has been interpreted qualitatively in terms of simple frontier molecular orbital theory. The -OH induced α-O-H deprotonation is consistent with a charge controlled reaction, whereas the C-H deprotonation, observed when the base is H2O, appears to be affected by frontier orbital interactions.
Visible-light photocatalytic selective oxidation of C(sp3)-H bonds by anion-cation dual-metal-site nanoscale localized carbon nitride
Duan, Limei,Li, Peihe,Li, Wanfei,Liu, Jinghai,Liu, Ying,Liu, Zhifei,Lu, Ye,Sarina, Sarina,Wang, Jinghui,Wang, Yin,Wang, Yingying,Zhu, Huaiyong
, p. 4429 - 4438 (2021/07/12)
Selective oxidation of C(sp3)-H bonds to carbonyl groups by abstracting H with a photoinduced highly active oxygen radical is an effective method used to give high value products. Here, we report a heterogeneous photocatalytic alkanes C-H bonds oxidation method under the irradiation of visible light (λ= 425 nm) at ambient temperature using an anion-cation dual-metal-site modulated carbon nitride. The optimized cation (C) of Fe3+or Ni2+, with an anion (A) of phosphotungstate (PW123?) constitutes the nanoscale dual-metal-site (DMS). With a Fe-PW12dual-metal-site as a model (FePW), we demonstrate a A-C DMS nanoscale localized carbon nitride (A-C/g-C3N4) exhibiting a highly enhanced photocatalytic activity with a high product yield (86% conversion), selectivity (up to 99%), and a wide functional group tolerance (52 examples). The carbon nitride performs the roles of both the visible light response, and improves the selectivity for the oxidation of C(sp3)-H bonds to carbonyl groups, along with the function of A-C DMS in promoting product yield. Mechanistic studies indicate that this reaction follows a radical pathway catalyzed by a photogenerated electron and hole on A-C/g-C3N4that is mediated by thetBuO˙ andtBuOO˙ radicals. Notably, a 10 g scale reaction was successfully achieved for alkane photocatalytic oxidation to the corresponding product with a good yield (80% conversion), and high selectivity (95%) under natural sunlight at ambient temperature. In addition, this A-C/g-C3N4photocatalyst is highly robust and can be reused at least six times and the activity is maintained.
Discovery of Chromane-6-Sulfonamide Derivative as a Potent, Selective, and Orally Available Novel Retinoic Acid Receptor-Related Orphan Receptor γt Inverse Agonist
Chen, Lei,Su, Mei,Jin, Qiu,Wang, Wei,Wang, Chun-Gu,Assani, Israa,Wang, Mu-Xuan,Zhao, Shi-Feng,Lv, Shen-Min,Wang, Jia-Wei,Sun, Bo,Li, Yan,Liao, Zhi-Xin
, p. 16106 - 16131 (2021/11/18)
Interleukin-17 (IL-17) is a proinflammatory cytokine that plays a dominant role in inflammation, autoimmunity, and host defense. RORγt is a key transcription factor mediating T helper 17 (Th17) cell differentiation and IL-17 production, which is able to activate CD8+ T cells and elicit antitumor efficacy. A series of sulfonamide derivatives as novel RORγt inverse agonists were designed and synthesized. Using GSK2981278 (phase II) as a starting point, we engineered structural modifications that significantly improved the activity and pharmacokinetic profile. In animal studies, oral administration of compound d3 showed a robust and dose-dependent inhibition of the IL-17A cytokine expression in a mouse imiquimod-induced skin inflammation model. Docking analysis of the binding mode revealed that the compound d3 occupied the active pocket suitably. Thus, compound d3 was selected as a clinical compound for the treatment of Th17-driven autoimmune diseases.
