1122-70-9Relevant articles and documents
AROMATIC HETEROCYCLIC SUBSTITUTED OLEFIN COMPOUND, PREPARATION METHOD FOR SAME, PHARMACEUTICAL COMPOSITION OF SAME, AND APPLICATIONS THEREOF
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Paragraph 0359-0361, (2021/02/05)
Provided in the present application are an aromatic heterocyclic substituted olefin compound, a preparation method for same, a pharmaceutical composition of same, and applications thereof. The aromatic heterocyclic substituted olefin compound of the present invention is a novel ALK5 inhibitor and is for use in treating and/or preventing various ALK5-mediated diseases.
An Electroreductive Approach to Radical Silylation via the Activation of Strong Si-Cl Bond
Lu, Lingxiang,Siu, Juno C.,Lai, Yihuan,Lin, Song
supporting information, p. 21272 - 21278 (2020/12/21)
The construction of C(sp3)-Si bonds is important in synthetic, medicinal, and materials chemistry. In this context, reactions mediated by silyl radicals have become increasingly attractive but methods for accessing these intermediates remain limited. We present a new strategy for silyl radical generation via electroreduction of readily available chlorosilanes. At highly biased potentials, electrochemistry grants access to silyl radicals through energetically uphill reductive cleavage of strong Si-Cl bonds. This strategy proved to be general in various alkene silylation reactions including disilylation, hydrosilylation, and allylic silylation under simple and transition-metal-free conditions.
Overcoming Selectivity Issues in Reversible Catalysis: A Transfer Hydrocyanation Exhibiting High Kinetic Control
Bhawal, Benjamin N.,Ehinger, Christian,Morandi, Bill,Reisenbauer, Julia C.
supporting information, p. 10914 - 10920 (2020/07/13)
Reversible catalytic reactions operate under thermodynamic control, and thus, establishing a selective catalytic system poses a considerable challenge. Herein, we report a reversible transfer hydrocyanation protocol that exhibits high selectivity for the thermodynamically less favorable branched isomer. Selectivity is achieved by exploiting the lower barrier for C-CN oxidative addition and reductive elimination at benzylic positions in the absence of a cocatalytic Lewis acid. Through the design of a novel type of HCN donor, a practical, branched-selective, HCN-free transfer hydrocyanation was realized. The synthetically useful resolution of a mixture of branched and linear nitrile isomers was also demonstrated to underline the value of reversible and selective transfer reactions. In a broader context, this work demonstrates that high kinetic selectivity can be achieved in reversible transfer reactions, thus opening new horizons for their synthetic applications.
Radical Hydroarylation of Functionalized Olefins and Mechanistic Investigation of Photocatalytic Pyridyl Radical Reactions
Seath, Ciaran P.,Vogt, David B.,Xu, Zihao,Boyington, Allyson J.,Jui, Nathan T.
supporting information, p. 15525 - 15534 (2018/11/23)
We report the photoredox alkylation of halopyridines using functionalized alkene and alkyne building blocks. Selective single-electron reduction of the halogenated pyridines provides the corresponding heteroaryl radicals, which undergo anti-Markovnikov addition to the alkene substrates. The system is shown to be mild and tolerant of a variety of alkene and alkyne subtypes. A combination of computational and experimental studies support a mechanism involving proton-coupled electron transfer followed by medium-dependent alkene addition and rapid hydrogen atom transfer mediated by a polarity-reversal catalyst.
Cobalt-catalyzed addition of styrylboronic acids to 2-vinylpyridine derivatives
Kobayashi, Tsuneyuki,Yorimitsu, Hideki,Oshima, Koichiro
supporting information; experimental part, p. 669 - 673 (2011/10/09)
Treatment of 2-vinyl nitrogen-containing heteroaromatic compounds with styrylboronic acid in the presence of a cobalt catalyst and a base results in an addition reaction to afford the corresponding 4-phenyl-3-butenyl heteroarenes. The adjacent nitrogen atom is essential for the promotion of the reaction because the nitrogen accelerates the addition of the styryl cobalt species, generated by transmetalation, onto the vinyl group. The reaction represents a rare example of cobalt catalysis in the reactions of organoboronic acids. Accelerated addition: Treatment of 2-vinylpyridine derivatives with styrylboronic acids under cobalt catalysis results in addition reactions. This represents a rare example of the cobalt-catalyzed reaction of organoboronic acids. Cobalt shows catalytic activity similar to rhodium, and catalyzes an unprecedented assembly of organoboronic acids and activated alkenes. Copyright
Process for preparing 2,6-divinylpyridine and 2-methyl-6-vinylpyridine from 2,6-lutidine over modified zeolites
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Page 2, (2008/06/13)
The present invention relates to a process for the preparation of 2,6-divinylpyridine and 2-methyl-6-vinylpyridine over modified zeolite catalysts. In particular, it relates to the method for the synthesis of 2,6-divinylpyridine and 2-methyl-6-vinylpyridine from 2,6-lutidine and formaldehyde in vapour phase in an eco-friendly method with high yield and selectivity. This invention provides a non-corrosive, eco-friendly process, where the catalyst can be reused for many times. 2,6-Divinylpyridine is useful stating material in polymer industry
PROCESS FOR PREPARING 2,6-DIVINYLPYRIDINE AND 2-METHYL-6-VINYLPYRIDINE FROM 2,6-LUTIDINE OVER MODIFIED ZEOLITES
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Page 4, (2008/06/13)
The present invention relates to a process for the preparation of 2,6-divinylpyridine and 2-methyl-6-vinylpyridine over modified zeolite catalysts. In particular, it relates to the method for the synthesis of 2,6-divinylpyridine and 2-methyl-6-vinylpyridine from 2,6-lutidine and formaldehyde in vapour phase in an eco-friendly method with high yield and selectivity. This invention provides a non-corrosive, eco-friendly process, where the catalyst can be reused for many times. 2,6-divinylpyridine is useful starting material in polymer industry.
Solid Phase Synthesis of 1,2-Disubstituted Alkenes: A Novel Alkynyldihydropyridine to Alkenylpyridine Isomerization
Chen, Chixu,Wang, Bowei,Munoz, Benito
, p. 2404 - 2406 (2007/10/03)
A series of 1,2-disubstituted pyridylalkenes have been prepared using a solid-phase resin approach. This approach takes advantage of a novel alkynyldihydropyridine to alkenylpyridine isomerization.
Synthesis and insertion chemistry of cationic zirconium (IV) pyridyl complexes. Productive σ-bond metathesis
Jordan, Richard F.,Taylor, Dennis F.,Baenziger, Norman C.
, p. 1546 - 1557 (2008/10/08)
The reaction of Cp2Zr(CH3)(THF)+ (1) with pyridine produces CH4 and a mixture of Cp2Zr(η2-N,C-pyridyl)(THF)+ (2) and Cp2Zr(η2-N,C-pyridyl)(pyridine)+ (3) via ortho-C-H bond activation. Complex 2 is converted to 3 by reaction with excess pyridine. Complex 1 reacts similarly with 2-methylpyridine (α-picoline) to yield the picolyl complex Cp2Zr{η2-N,C-NC5H 3(6-Me)}(THF)+ (6). An intermediate picoline adduct Cp2Zr(CH3)(picoline)+ (7a) is observed in this reaction. Low-temperature NMR studies of 7a and the (C5H4Me)2Zr analogue 7b reveal a high-field 1H shift and a reduced JC-H for the ortho C-H of the coordinated picoline suggestive of an agostic interaction. The three-membered Zr-N-C ring structures of 2, 3, and 6 are assigned on the basis of 1H and 13C NMR spectral data and confirmed by X-ray crystallographic analysis of Cp2Zr{η2-N,C-NC5H 3(6-Me)}(PMe3)+ (8), which is formed by reaction of 6 with PMe3. Complex 8 crystallizes in space group Cc with a = 9.571 (4) A?, b = 17.524 (11) A?, c = 21.861 (7) A?, β = 92.55 (3)°, V = 3662.9 (5.1) A?3, and Z = 4. The picolyl ligand of 8 lies in the plane between the two Cp ligands, and the Zr-C (2.29 (2) A?) and Zr-N (2.21 (1) A?) bond lengths are similar. Complex 6 reacts readily with ethylene, propylene, and 2-butyne to yield insertion products 9-11, which have five-membered chelate ring structures. These reactions proceed via initial THF dissociation from 6 followed by coordination of substrate and insertion into the Zr-C bond. Complex 9 crystallizes in space group P1 with a = 10.387 (2) A?, b = 12.129 (3) A?, c = 13.844 (4) A?, α = 87.78 (2)°, β = 76.37 (2)°, γ = 76.63 (2)°, V = 1648.8 (9) A?3, and Z = 2. The chelate ring of 9 is relatively unstrained. Complexes 9 and 10 react with CH3CN to yield 2-ethenyl-6-methylpyridine and 2-(1-methylethenyl)-6-methylpyridine (14), respectively, and Cp2Zr(N= CHMe)(CH3CN)+ (13). These reactions proceed by ligand-induced ring opening, β-H elimination, and trapping of the Zr-H product by CH3CN insertion. Complex 10 reacts similarly with PMe3 to yield 14 and Cp2Zr(H)(PMe3)2+ (17) via ring opening, β-H elimination, and trapping of the Zr-H product by PMe3 coordination. These Zr-mediated olefin/picoline coupling reactions illustrate how productive reaction schemes may be constructed by combining σ-bond metathesis, insertion, and β-H elimination reactions.
