22381-56-2Relevant academic research and scientific papers
Site-Selective 1,4-Difunctionalization of Nitrogen Heteroaromatics for Constructing Vinylidene Heterocycles
Chen, Xiuwen,Chen, Zhichao,He, Qianlin,Liao, Chuyi,Xie, Feng,Zhong, Mingli,Zhu, Zhongzhi
supporting information, p. 459 - 463 (2021/12/14)
A one-pot protocol for constructing 1,4-difunctionalized quinoline/pyridine derivatives via the reaction of N-heteroaromatics, alkyl halides, and active methylene/methyl compounds was developed. The transformation involves dearomative functionalization of
Design, synthesis and application of spiro[4.5]cyclohexadienonesviaone-pot sequentialp-hydroxybenzylation/oxidative dearomatization
Patil, Vaibhav B.,Nanubolu, Jagadeesh Babu,Chegondi, Rambabu
supporting information, p. 5574 - 5577 (2021/06/12)
One-pot sequentialp-hydroxybenzylation/oxidative dearomatization/spiroannulation has been designed for the efficient construction of tetrahydrofuran containing spiro-cyclohexadienones. This reaction proceeds through thep-hydroxybenzylation of 1,3-diketones withp-hydroxybenzyl alcoholviaquinone methide formation followed by oxidative dearomatization/spiroannulation with suitable alcohols. The Friedel-Crafts alkylation of spiro[4.5]cyclohexadienones with indoles provided a broad array of highly diastereoselective C-3 alkylated spirocycles and cyclohepta[b]indoles depending upon the ring size of the fused cyclic ketones.
Copper-Nitrene-Catalyzed Desymmetric Oxaziridination/1,2-Alkyl Rearrangement of 1,3-Diketones toward Bicyclic Lactams
Han, Xue,Shan, Li-Xin,Tu, Yong-Qiang,Wang, Hong,Yang, Ming,Zhang, Chang-Sheng,Zhang, Fu-Min,Zhang, Wen-Shuo,Zhang, Xiao-Ming,Zhu, Jin-Xin
supporting information, p. 22688 - 22692 (2021/09/18)
Although copper-nitrene has been extensively studied as a versatile active species in various transformations, asymmetric reactions involving copper-nitrene have been limited to the aziridination of olefins. Herein, we report the novel copper-nitrene-catalyzed desymmetric oxaziridination reaction of cyclic diketones with alkyl azides and the subsequent rearrangement of the resulting highly active intermediate, which produces a synthetically challenging chiral bicyclic lactam containing a quaternary carbon center. This procedure not only enriches the copper-nitrene-catalyzed asymmetric reactions, but also provides an alternative strategy to address the inherent challenges of catalytic asymmetric Schmidt reactions. This unique reaction could inspire the investigation of novel copper-nitrene-catalyzed asymmetric transformations and their reaction mechanisms.
Nickel-catalyzed intramolecular desymmetrization addition of aryl halides to 1,3-diketones
Xu, Tao,Zhou, Pan
supporting information, p. 8194 - 8197 (2020/08/17)
A nickel-catalyzed intramolecular addition of aryl halides to 1,3-diketones was first developed. This desymmetrization reaction afforded polycyclic products bearing two tetrasubstituted centers with excellent diastereoselectivities and high yields. Moderate enantioselectivities were achieved in the presence of a chiral ligand. This transformation has great potential for the synthesis of polycyclic compounds including spiro[4,4,3,0] compounds. This journal is
Photolabile beta-dicarbonyl compounds
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Paragraph 0115, (2020/02/18)
The present disclosure provides a redox initiator system for initiating polymerization comprising an oxidizing agent, a photolabile reducing agent, and a transition metal complex that participates in a redox cycle. On exposure to actinic radiation, such as UV, the photolabile compound photolyzes, releasing the reducing agent and initiating the redox-initiated polymerization.
Synthesis of N-Fused Polycyclic Indoles via Ligand-Free Palladium-Catalyzed Annulation/Acyl Migration Reaction
Dong, Zhan,Zhang, Xiao-Wen,Li, Weishuang,Li, Zi-Meng,Wang, Wen-Yan,Zhang, Yan,Liu, Wei,Liu, Wen-Bo
supporting information, p. 1082 - 1086 (2019/02/14)
An efficient synthesis of N-fused polycyclic indoles by a palladium-catalyzed annulation/acyl migration cascade reaction is described. The reaction is ligand-free, scalable, and provides access to a diverse range of useful indole scaffolds from readily available starting materials. Supporting mechanistic studies indicate that the reaction likely proceeds via an intramolecular α-arylation mechanism. The synthetic utility of this protocol is demonstrated by a gram-scale reaction and syntheses toward indole alkaloids and a HSP90 inhibitor.
Enantioselective Copper-Catalyzed Desymmetrization of 1,3-Diketones Involving Borylation of Styrenes
Zheng, Purui,Han, Xiaoyu,Hu, Jiao,Zhao, Xiaoming,Xu, Tao
supporting information, p. 6040 - 6044 (2019/08/27)
A copper-catalyzed intramolecular enantioselective and diastereoselective borylative coupling of styrenes and ketones was achieved by merging desymmetrization strategy and olefin difunctionalization. The reaction proceeds through an initial enantioselective borylcupration of styrenes, followed by a highly selective direct addition to 1,3-diketones. The bicyclic scaffolds with three chiral carbon centers, including two tetrasubstituted carbons, were generated in excellent yields, diastereoselectivities, and enantioselectivities. This catalytic tandem reaction has great potential for further synthetic application of the chiral polycyclic compounds, because of the versatility of the functional groups in the products.
Structure-dependent selective O- or C-trifluoroethylation of 1,3-dicarbonyls by mesityl(2,2,2-trifluoroethyl)iodonium triflate
Zhao, Cheng-Long,Yang, Jing,Han, Zhou-Zhou,Zhang, Cheng-Pan
supporting information, p. 23 - 30 (2017/10/30)
Reaction of [ArICH2CF3][OTf] with structurally diversified 1,3-dicarbonyls and an appropriate base at room temperature gave O-trifluoroethylated products, C-trifluoroethylated products, or a mixture of O- and C-trifluoroethylated products in good yields. The product type was dramatically dependent upon the structure of the starting 1,3-dicarbonyls in this reaction. The cyclic 1,3-diketones exclusively afforded the O-trifluoroethylated products, whereas the acyclic 1,3-diketones, β-keto esters, and malonates selectively or specifically formed the C-trifluoroethylated products. Li2CO3 facilitated the C-trifluoroethylation of acyclic 1,3-diketones and β-keto esters. The reaction proceeded under mild conditions, without pre-activation of 1,3-dicarbonyls and use of strong base, and demonstrated a catalyst-free structure-dependent regioselective trifluoroethylation of 1,3-dicarbonyls by mesityl(2,2,2-trifluoroethyl)iodonium triflate.
Forging Fluorine-Containing Quaternary Stereocenters by a Light-Driven Organocatalytic Aldol Desymmetrization Process
Cuadros, Sara,Dell'Amico, Luca,Melchiorre, Paolo
supporting information, p. 11875 - 11879 (2017/09/20)
Reported herein is a light-triggered organocatalytic strategy for the desymmetrization of achiral 2-fluoro-substituted cyclopentane-1,3-diketones. The chemistry is based on an intermolecular aldol reaction of photochemically generated hydroxy-o-quinodimethanes and simultaneously forges two adjacent fully substituted carbon stereocenters, with one bearing a stereogenic carbon–fluorine unit. The method uses readily available substrates, a simple chiral organocatalyst, and mild reaction conditions to afford an array of highly functionalized chiral 2-fluoro-3-hydroxycyclopentanones.
Enantioselective Palladium-Catalyzed Intramolecular α-Arylative Desymmetrization of 1,3-Diketones
Zhu, Chendan,Wang, Dingyi,Zhao, Yue,Sun, Wei-Yin,Shi, Zhuangzhi
supporting information, p. 16486 - 16489 (2017/11/30)
An efficient enantioselective protocol has been reported to build highly oxygenated and densely substituted bicyclo[m.n.1] skeletons through intramolecular asymmetric α-arylative desymmetrization of 1,3-diketones. Employing Pd catalyst and FOXAP ligand, various bicyclo[m.n.1] skeleton with different size can be accessed with high enantio- and diastereoselectivities. Utilizing the present method as a key step, formal asymmetric total synthesis of the (-)-parvifoline has been demonstrated.
