13615-40-2Relevant articles and documents
Carbon-Hydrogen and C-X (X=Cl or SiMe3) Bond Activation. 1-Cyclopalladation and Oxidation of Some Derivatives of 2-naphthalene
Valk, Jean-Marc,Belzen, Ruud van,Boersma, Jaap,Spek, Anthony L.,Koten, Gerard van
, p. 2293 - 2302 (1994)
The regioselective palladation reactions of 3-substituted derivatives of 2-naphthalene, C10H6(CH2NMe2)-2-R-3 (R=Cl, SiMe3 or OSiMe3), were studied.For the substrate with R=Cl, no cyclopalladation at position 1 was observed and the co-ordination complex was isolated.The 3-palladated product was formed in 10percent yield via C-Cl activation.The reaction of 2--3-methylnaphthalene with Pd(O2CMe)2 and work-up with LiCl did lead to palladation at position 1, the resulting complex being isolated in 96percent yield.The crystal structure of bis(acetonitrile) -3-methyl-1-naphthyl>palladium trifluoromethanesulfonate was solved.Monoclinic, space group P21/n, with a=13.193(1), b=11.801(1), c=14.797(1) Angstroem, β=105.15(1) deg, Z=4.The structure was refined to R=0.042 for 3455 reflections with I > 2.5?(I).Palladation at position 1 was also achieved by oxidative addition of 1-bromo-2-naphthalene to (dba=dibenzylideneacetone).Protection of C(3) with R=SiMe3 resulted in quantitative replacement of the SiMe3 group by palladium.Silicon-oxygen bond cleavage was observed when the substrate with R=OSiMe3 was treated with Pd(O2CMe)2.Palladium bis-2-naphtholate> was obtained quantitatively.Oxidation of several arylpalladium complexes with tBuO2H was achieved in the presence of (acac=acetylacetonate) or 2> (cod=cycloocta-1,5-diene) as catalyst.The corresponding 1-naphthols were prepared in yields varying from 33 to 78 percent.In a number of cases the corresponding 1,4-naphthoquinones were prepared in yields varying from 18 to 38percent.
A Novel Palladium- or Platinum-Catalyzed Cyclocarbonylation Reaction of Cinnamyl Compounds for Synthesis of 1-Naphthol Derivatives
Matsuzaka, Hiroyuki,Hiroe, Yoshitaka,Iwasaki, Masakazu,Ishii, Youichi,Koyasu, Yukio,Hidai, Masanobu
, p. 3832 - 3838 (1988)
Cinnamyl compounds undergo smooth cyclocarbonylation to afford 1-naphthol derivatives at 160 deg C under 60 atm of CO in the presence of Ac2O, NEt3, and a catalytic amount of palladium- or platinum-phosphine complexes.Similar cyclocarbonylation of 3-(2'-naphthyl)allyl acetate selectively proceeds to give 4-phenanthryl acetate.The mechanistic investigation reveals that cyclocarbonylation of cinnamyl compounds proceeds through the intramolecular attack on the aromatic ring by the acyl moiety of the intermediary (Z)-4-aryl-2- or -3-butenoyl-palladium complex, which is formed by oxidative addition of cinnamyl compounds to a Pd(0) species followed by CO insertion into the Pd-C bond of the δ-allyl intermediate and carbon-carbon double-bond migration.
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Sepiol,J.,Mirek,J.
, p. 290 - 292 (1979)
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Novel biphasic reaction system of ferric chloride dissolved imidazolium hexafluorophosphate and benzotrifluoride: application to electron transfer reaction of cyclopropyl silyl ethers
Tsuchida, Hiroyuki,Hasegawa, Eietsu
, p. 3447 - 3451 (2010)
Ferric chloride (FeCl3) promoted electron transfer oxidation of bicyclic cyclopropyl silyl ethers was performed in biphasic solution system of 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF6) and benzotrifluoride (BTF). The resulting chloro-substituted ring-expanded cycloalkanones were treated with an appropriate base to produce substituted cyclic enones. These two-step reactions were successfully devised to proceed in a simpler manner in which the ordinary work-up operations for the former oxidation step, such as water-quench, extraction, and evaporation, were omitted; imidazole was found to be the most suitable base for the latter elimination step.
KRAS G12C INHIBITORS
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Paragraph 0474, (2020/07/25)
The present invention relates to compounds that inhibit KRas G12C. In particular, the present invention relates to compounds that irreversibly inhibit the activity of KRas G12C, pharmaceutical compositions comprising the compounds and methods of use therefor.
Intramolecular carbonyl-ene reactions in the synthesis of peri-oxygenated hydroaromatics
Basak, Shyam,Mal, Dipakranjan
, p. 1758 - 1772 (2018/03/29)
2-Methallyl aromatic aldehydes, synthesized by Suzuki coupling of 2-formylphenylboronic acids, are shown to provide cycloalkylidene ene products under acidic conditions. Susceptibility of the products to aromatization is manoeuvred by varying the reaction conditions and catalysts including binol-derived Br?nsted acid catalysts. A peri-effect is identified as a controlling factor for the aromatizations. Several oxidative transformations of an ene product are carried out as model studies of hydroaromatic polyketide natural products.
