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.
Tris(trimethylsilyl)silane promoted radical reaction and electron-transfer reaction in benzotrifluoride
Hasegawa, Eietsu,Ogawa, Yuki,Kakinuma, Koji,Tsuchida, Hiroyuki,Tosaka, Emi,Takizawa, Shinya,Muraoka, Hiroyasu,Saikawa, Tomoko
, p. 7724 - 7728 (2008)
Tris(trimethylsilyl)silane (TTMSS) promoted free radical reaction in benzotrifluoride (BTF) was investigated. Compared to same reaction using environmentally less desirable tri-n-butyltin hydride (TBTH) in benzene, less quantity of BTF than that of benzene can be used because of slower hydrogen atom transfer from TTMSS than that from TBTH toward primary alkyl radicals. Also, electron-transfer reactions promoted by tris(p-bromophenyl)aminium hexachloroantimonate (TBPA) and FeCl3 were conducted in BTF. Then, TBPA was found to be effective in BTF comparably to that in methylene chloride. In addition, an interesting observation that FeCl3 promoted reaction was accelerated by the addition of imidazolium salt was made. All the results suggest that BTF is a tolerable solvent for free radical reaction with TTMSS and electron-transfer reactions using TBPA as well as FeCl3.
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.
ION CHANNEL ANTAGONISTS/BLOCKERS AND USES THEREOF
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Page/Page column 24; 40; 41, (2021/06/22)
Provided are ion channel antagonists/blockers and uses thereof. Specifically, it provides the compounds of formula (I) or pharmaceutically acceptable salts, stereoisomers, solvates or prodrugs, preparation method therefor and application thereof. Definition of each group in the formula can be found in the specification for details. Provided is also pharmaceutical composition useful for treatment of heart disease and other ion channel related diseases.
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.
TRANSITION METAL FREE METHODS OF SYNTHESIS OF BIARYL COMPOUNDS
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Page/Page column 38, (2017/06/21)
The present disclosure provides methods of preparing biaryl compounds which do not require transition metal catalysts. In yet another aspect, the present disclosure provides pharmaceutical compositions comprising compounds as described herein and pharmaceutically acceptable carriers.
Solvent-Dependent Reaction Pathways Operating in Copper(II) Tetrafluoroborate Promoted Oxidative Ring-Opening Reactions of Cyclopropyl Silyl Ethers
Hasegawa, Eietsu,Nemoto, Kazuki,Nagumo, Ryosuke,Tayama, Eiji,Iwamoto, Hajime
, p. 2692 - 2703 (2016/04/26)
(Figure Presented) Oxidative ring-opening reactions of benzene-fused bicyclic cyclopropyl silyl ethers, promoted by copper(II) tetrafluoroborate, were investigated. The regioselectivity of cyclopropane ring-opening as well as product distributions were found to be highly dependent on the nature of the solvent. In alcohols, dimeric substances arising from external bond cleavage are major products. Radical rearrangement products are also formed in solvents such as ether and ethyl acetate. On the contrary, nucleophile addition to carbocation intermediates, generated by internal bond cleavage, occurs mainly in reactions taking place in acetonitrile. It is proposed that the observed solvent effects that govern the reaction pathways followed are a consequence of varying solvation of copper intermediates, which governs their reactivity and redox properties. In addition, the influence of counteranions of the copper salts, organonitriles, cyclic dienes, and substrate structures on the pathways followed in these reactions was also examined.
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.
Facile synthesis of 1-naphthols through a copper-catalyzed arylation of methyl ketones with o-bromoacetophenones
Lou, Zhen-Bang,Pang, Xin-Long,Chen, Chao,Wen, Li-Rong,Li, Ming
supporting information, p. 1231 - 1235 (2015/12/30)
The coupling reactions of simple methyl ketones with o-bromoacetophenones and subsquential cyclization reactions were realized to produce a range of 1-naphthols. These cascade reactions were initiated by a rare Cu-catalyzed arylation reaction of methyl ketones with aromatic bromides.
