288632-71-3Relevant academic research and scientific papers
Enantioenriched 1-Tetralones via Rhodium-Catalyzed Arylative Cascade Desymmetrization/Acylation of Alkynylmalonates
Selmani, Aymane,Darses, Sylvain
, p. 8122 - 8126 (2019)
An efficient atom-economic rhodium-catalyzed asymmetric arylative cyclization to access enantioenriched 1-tetralones, bearing a quaternary carbon stereocenter, is described, involving a highly regioselective alkyne insertion, a 1,4-Rh shift, and an acylation step via the desymmetrization of the malonate moiety thanks to an appropriate chiral diene ligand.
A gallium-catalyzed cycloisomerization/Friedel-Crafts tandem
Li, Hui-Jing,Guillot, Regis,Gandon, Vincent
supporting information; experimental part, p. 8435 - 8449 (2011/03/19)
Under noble (Au, Pt, Ru) and group 13 (Ga, In) metals catalysis, 1,6-arenynes rearrange to give 1,2-dihydronaphthalenes in a high yielding, regiocontrolled fashion. When the reaction is carried out in the presence of electron-rich arenes (anisole, phenol, indole derivatives), Friedel-Crafts addition may follow the cycloisomerization step. Only GaX3 salts proved able to catalyze these two C-C bond formation events. This specificity of gallium has been exploited for the synthesis of valuable polycyclic compounds that would be very difficult to prepare otherwise. For instance, tetrahydroisoquinolines and tetrahydrobenzoazepines have been obtained by selective 6-exo-dig or 7-endo-dig cyclization of N-tethered 1,6-arenynes. DFT calculations were carried out to shed light on the mechanism and provide a rationale for this regiodivergency. Computations also reveal the fundamental role of the tether in the stabilization of carbocationic species. Differential reactivities of other types of substrates in gallium- and gold-catalyzed cascades are also exposed, showing that the two approaches are complementary. In particular, bimolecular Friedel-Crafts additions are facilitated under gallium catalysis.
Highly efficient synthesis of functionalized dihydronaphthalenes, tetrahydronaphthalenes, and tetrahydroisoquinolines by iron-catalyzed intramolecular Friedel-Crafts reaction of aryl-containing propargylic alcohols
Huang, Wen,Hong, Longcheng,Zheng, Pengzhi,Liu, Ruiting,Zhou, Xigeng
body text, p. 3603 - 3610 (2009/09/06)
An efficient, convenient, and one-pot procedure for the synthesis of a series of new dihydro- and tetrahydronaphthalenes as well as tetrahydroisoquinolines has been established through Lewis acid-catalyzed intramolecular Friedel-Crafts reaction of aryl-substituted propargylic alcohols.
Design, synthesis, and structure-activity relationships of haloenol lactones: Site-directed and isozyme-selective glutathione S-transferase inhibitors
Wu, Zhixing,Minhas, Gurpreet Singh,Wen, Dingyi,Jiang, Hualiang,Chen, Kaixian,Zimniak, Piotr,Zheng, Jiang
, p. 3282 - 3294 (2007/10/03)
Overexpression of glutathione S-transferase (GST), particularly the GST-π isozyme, has been proposed to be one of the biochemical mechanisms responsible for drug resistance in cancer chemotherapy, and inhibition of overexpressed GST has been suggested as an approach to combat GST-induced drug resistance. 3-Cinnamyl-5(E)-bromomethylidenetetrahydro-2-furanone (1a), a lead compound of site-directed GST-π inactivator, has been shown to potentiate the cytotoxic effect of cisplatin on tumor cells. As an initial step to develop more potent and more selective haloenol lactone inactivators of GST-π, we examined the relationship between the chemical structures of haloenol lactone derivatives and their GST inhibitory activity. A total of 16 haloenol lactone derivatives were synthesized to probe the effects of (1) halogen electronegativity, (2) electron density of aromatic rings, (3) molecular size and rigidity, (4) lipophilicity, and (5) aromaticity on the potency of GST-π inactivation. The inhibitory potency of each compound was determined by time-dependent inhibition tests, and recombinant human GST-π was used to determine their inhibitory activity. Our structure-activity relationship studies demonstrated that (1) reactivity of the halide leaving group plays a weak role in GST inactivation by the haloenol lactones, (2) aromatic electron density may have some influence on the potency of GST inactivation, (3) high rigidity likely disfavors enzyme inhibition, (4) lipophilicity is inversely proportional to enzyme inactivation, and (5) an unsaturated system may be important for enzyme inhibition. This work facilitated understanding of the interaction of GST-π with haloenol lactone derivatives as site-directed and isozyme-selective inactivators, possibly potentiating cancer chemotherapy.
Ru(II)- and Pt(II)-catalyzed cycloisomerization of ω-Aryl-1-alkynes. Generation of carbocationic species from alkynes and transition metal halides and its interception by an aromatic ring
Chatani, Naoto,Inoue, Hiroki,Ikeda, Tsutomu,Murai, Shinji
, p. 4913 - 4918 (2007/10/03)
The treatment of aryl-1-alkynes, such as 4-aryl-1-butyne, 5-aryl-1-pentyne, and 6-aryl-1-hexyne, with catalytic amounts of transition metal chlorides, such as PtCl2 and [RuCl2(CO)3]2, at 80 °C in toluene results in cycloisomerization to give dihydronaphthalenes or dihydrobenzocycloheptenes, in which the cyclization mode is dependent on the length of the tethers. The reaction is limited to substrates containing terminal alkynes. A key step of the reaction is the intramolecular interception by an aromatic ring of the vinylmetal complex 2, which contains a cation center at the β-position, generated from the electrophilic addition of transition metal halides toward an alkyne. The more electron-rich aryl systems are more reactive.
