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31.
Xi‐Sha Zhang Yun‐Fei Zhang Zhao‐Wei Li Fei‐Xian Luo Zhang‐Jie Shi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(18):5568-5572
A rhodium(III)‐catalyzed cross‐coupling of benzyl thioethers and aryl carboxylic acids through the two directing groups is reported. Useful structures with diverse substituents were efficiently synthesized in one step with the cleavage of four bonds (C H, C S, O H) and the formation of two bonds (C C, C O). The formed structure is the privileged core in natural products and bioactive molecules. This work highlights the power of using two different directing groups to enhance the selectivity of a double C H activation, the first of such examples in cross‐oxidative coupling. 相似文献
32.
Srigokul Upadhyayula Vicente Nu?ez Eli M. Espinoza Jillian M. Larsen Duoduo Bao Dewen Shi Jenny T. Mac Bahman Anvari Valentine I. Vullev 《Chemical science》2015,6(4):2237-2251
Cyanine dyes are broadly used for fluorescence imaging and other photonic applications. 3,3′-Diethylthiacyanine (THIA) is a cyanine dye composed of two identical aromatic heterocyclic moieties linked with a single methine, –CH. The torsional degrees of freedom around the methine bonds provide routes for non-radiative decay, responsible for the inherently low fluorescence quantum yields. Using transient absorption spectroscopy, we determined that upon photoexcitation, the excited state relaxes along two parallel pathways producing three excited-state transients that undergo internal conversion to the ground state. The media viscosity impedes the molecular modes of ring rotation and preferentially affects one of the pathways of non-radiative decay, exerting a dominant effect on the emission properties of THIA. Concurrently, the polarity affects the energy of the transients involved in the decay pathways and further modulates the kinetics of non-radiative deactivation. 相似文献
33.
Visible‐Light‐Induced Trifluoromethylation of Isonitrile‐Substituted Methylenecyclopropanes: Facile Access to 6‐(Trifluoromethyl)‐7,8‐Dihydrobenzo[k]phenanthridine Derivatives 下载免费PDF全文
Yu‐Chao Yuan Hou‐Lu Liu Xu‐Bo Hu Prof. Dr. Yin Wei Prof. Dr. Min Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(37):13059-13063
A new visible‐light‐induced trifluoromethylation of isonitrile‐substituted methylenecyclopropanes is developed. A range of substituted 6‐(trifluoromethyl)‐7,8‐dihydrobenzo[k]phenanthridine derivatives are readily furnished by this newly developed tandem reaction with moderate to good yields. This reaction allows the direct formation of two six‐membered rings and three new C?C bonds, including the C?CF3 bond, under visible light irradiation. 相似文献
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Kinetic Resolution of Racemic Allylic Alcohols by Catalytic Asymmetric Substitution of the OH Group with Monosubstituted Hydrazines 下载免费PDF全文
Liang Yan Jing‐Kun Xu Chao‐Fan Huang Zeng‐Yang He Ya‐Nan Xu Prof. Dr. Shi‐Kai Tian 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(37):13041-13045
A new strategy has been established for the kinetic resolution of racemic allylic alcohols through a palladium/sulfonyl‐hydrazide‐catalyzed asymmetric OH‐substitution under mild conditions. In the presence of 1 mol % [Pd(allyl)Cl]2, 4 mol % (S)‐SegPhos, and 10 mol % 2,5‐dichlorobenzenesulfonyl hydrazide, a range of racemic allylic alcohols were smoothly resolved with selectivity factors of more than 400 through an asymmetric allylic alkylation of monosubstituted hydrazines under air at room temperature. Importantly, this kinetic resolution process provided various allylic alcohols and allylic hydrazine derivatives with high enantiopurity. 相似文献
39.
An Unprecedented Two‐Fold Nested Super‐Polyrotaxane: Sulfate‐Directed Hierarchical Polythreading Assembly of Uranyl Polyrotaxane Moieties 下载免费PDF全文
Dr. Lei Mei Dr. Qun‐yan Wu Dr. Li‐yong Yuan Dr. Lin Wang Shu‐wen An Zhen‐ni Xie Dr. Kong‐qiu Hu Prof. Zhi‐fang Chai Prof. Peter C. Burns Prof. Wei‐qun Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(32):11329-11338
The hierarchical assembly of well‐organized submoieties could lead to more complicated superstructures with intriguing properties. We describe herein an unprecedented polyrotaxane polythreading framework containing a two‐fold nested super‐polyrotaxane substructure, which was synthesized through a uranyl‐directed hierarchical polythreading assembly of one‐dimensional polyrotaxane chains and two‐dimensional polyrotaxane networks. This special assembly mode actually affords a new way of supramolecular chemistry instead of covalently linked bulky stoppers to construct stable interlocked rotaxane moieties. An investigation of the synthesis condition shows that sulfate can assume a vital role in mediating the formation of different uranyl species, especially the unique trinuclear uranyl moiety [(UO2)3O(OH)2]2+, involving a notable bent [O=U=O] bond with a bond angle of 172.0(9)°. Detailed analysis of the coordination features, the thermal stability as well as a fluorescence, and electrochemical characterization demonstrate that the uniqueness of this super‐polyrotaxane structure is mainly closely related to the trinuclear uranyl moiety, which is confirmed by quantum chemical calculations. 相似文献
40.
Efficient Synthesis of Diaryl Ketones by Nickel‐Catalyzed Negishi Cross‐Coupling of Amides by Carbon–Nitrogen Bond Cleavage at Room Temperature Accelerated by a Solvent Effect 下载免费PDF全文
Shicheng Shi Prof. Dr. Michal Szostak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(30):10420-10424
The first Negishi cross‐coupling of amides for the synthesis of versatile diaryl ketones by selective C?N bond activation under exceedingly mild conditions is reported. The cross‐coupling was accomplished with bench‐stable, inexpensive precatalyst [Ni(PPh3)2Cl2] that shows high functional‐group tolerance and enables the synthesis of highly functionalized diaryl ketone motifs. The coupling occurred with excellent chemoselectivity favoring the ketone (cf. biaryl) products. Notably, this process represents the mildest conditions for amide N?C bond activation accomplished to date (room temperature, <10 min). Considering the versatile role of polyfunctional biaryl ketone linchpins in modern organic synthesis, availability, and excellent functional‐group tolerance of organozinc reagents, this strategy provides a new platform for amide N?C bond/organozinc cross‐coupling under mild conditions. 相似文献