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81.
82.
Ram Ambre Ting-Hsuan Wang Anmei Xian Yu-Shiuan Chen Yu-Fu Liang Prof. Titel Jurca Prof. Lili Zhao Prof. Tiow-Gan Ong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(71):17021-17026
A simple Ni(cod)2 and carbene mediated strategy facilitates the efficient catalytic cross-coupling of methoxyarenes with a variety of organoboron reagents. Directing groups facilitate the activation of inert C−O bonds in under-utilized aryl methyl ethers enabling their adaptation for C−C cross-coupling reactions as less toxic surrogates to the ubiquitous haloarenes. The method reported enables C−C cross-coupling with readily available and economical arylboronic acid reagents, which is unprecedented, and compares well with other organoboron reagents with similarly high reactivity. Extension to directing group assisted chemo-selective C−O bond cleavage, and further application towards the synthesis of novel bifunctionalized biaryls is reported. Key to the success of this protocol is the use of directing groups proximal to the reaction center to facilitate the activation of the inert C−OMe bond. 相似文献
83.
Pierre Thesmar Seemon Coomar Dr. Alessandro Prescimone Prof. Dr. Daniel Häussinger Prof. Dr. Dennis Gillingham Prof. Dr. Olivier Baudoin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(66):15298-15312
This article provides a detailed report of our efforts to synthesize the dithiodiketopiperazine (DTP) natural products (−)-epicoccin G and (−)-rostratin A using a double C(sp3)−H activation strategy. The strategy's viability was first established on a model system lacking the C8/C8’ alcohols. Then, an efficient stereoselective route including an organocatalytic epoxidation was secured to access a key bis-triflate substrate. This bis-triflate served as the functional handles for the key transformation of the synthesis: a double C(sp3)−H activation. The successful double activation opened access to a common intermediate for both natural products in high overall yield and on a multigram scale. After several unsuccessful attempts, this intermediate was efficiently converted to (−)-epicoccin G and to the more challenging (−)-rostratin A via suitable oxidation/reduction and protecting group sequences, and via a final sulfuration that occurred in good yield and high diastereoselectivity. These efforts culminated in the synthesis of (−)-epicoccin G and (−)-rostratin A in high overall yields (19.6 % over 14 steps and 12.7 % over 17 steps, respectively), with the latter being obtained on a 500 mg scale. Toxicity assessments of these natural products and several analogues (including the newly synthesized epicoccin K) in the leukemia cell line K562 confirmed the importance of the disulfide bridge for activity and identified dianhydrorostratin A as a 20x more potent analogue. 相似文献
84.
Physical properties of titanates,semiconductors and nickelates derived from ionization energy theory
《Physics letters. A》2020,384(36):126917
Ionization energy theory is exploited to predict the changes to atomic polarizability for both anions and cations, the polarization in doped titanates and the energy gap in III–V and II–VI semiconductors. We then extend the above analysis to discuss the physics of metallic and superconducting phases in the recently discovered superconducting nickelates. In doing so, we are able to prove the existence of Ni2+ cations and oxygen vacancy in the metallic normal state of nickelates. We find that the normal state resistivity of the nickelates follows exactly as predicted by the ionization energy theory. Quantitative estimates are also given for the concentrations of Ni2+ and oxygen vacancy in superconducting nickelates. 相似文献
85.
Dr. Shao-Ping Zheng Dr. Ji-Jun Jiang Dr. Arie van der Lee Dr. Mihail Barboiu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(43):19082-19088
Transmembrane protein channels are an important inspiration for the design of artificial ion channels. Their dipolar structure helps overcome the high energy barrier to selectively translocate water and ions sharing one pathway, across the cell membrane. Herein, we report that the amino-imidazole (Imu) amphiphiles self-assemble via multiple H-bonding to form stable artificial Cl−-channels within lipid bilayers. The alignment of water/Cl− wires influences the conduction of ions, envisioned to diffuse along the hydrophilic pathways; at acidic pH, Cl−/H+ symport conducts along a partly protonated channel, while at basic pH, higher Cl−/OH− antiport translocate through a neutral channel configuration, which can be greatly activated by applying strong electric field. This voltage/pH regulated channel system represents an unexplored alternative for ion-pumping along artificial ion-channels, parallel to that of biology. 相似文献
86.
Dr. Gang Liao Dr. Tao Zhang Zhi-Keng Lin Prof. Dr. Bing-Feng Shi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(45):19941-19954
Transition metal-catalyzed enantioselective functionalization of C−H bond, the most abundant functionality in organic molecules, has emerged as an expedient synthetic approach to streamline the synthesis of complex chiral molecules. Despite significant progress, traditional directing group-enabled strategies require additional steps for the installation and removal of directing groups from the target molecule. The recently developed asymmetric C−H functionalization using chiral transient directing groups (cTDGs) offers a promising alternative that can circumvent this obstacle and therefore simplify the process. In this Minireview, we briefly discuss the advent and recent advances of this emerging concept, with an emphasis on discussing the creation of various stereogenic centers and the developments of cTDGs. Applications in natural product synthesis and ligand derivatizations are also discussed. We hope this Minireview will highlight the great potential of this strategy and help to inspire further endeavors. 相似文献
87.
Tomáš Čarný Dr. Ronan Rocaboy Dr. Antonin Clemenceau Prof. Dr. Olivier Baudoin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(43):19142-19146
The 1,4-palladium shift strategy allows the functionalization of remote C−H bonds that are difficult to reach directly. Reported here is a domino reaction proceeding by C(sp3)−H activation, 1,4-palladium shift, and amino- or alkoxycarbonylation, which generates a variety of amides and esters bearing a quaternary β-carbon atom. Mechanistic studies showed that the aminocarbonylation of the σ-alkylpalladium intermediate arising from the palladium shift is fast using PPh3 as the ligand, and leads to the amide rather than the previously reported indanone product. 相似文献
88.
Honghua Zhang Huihong Wang Yi Jiang Fei Cao Weiwei Gao Longqing Zhu Yuhang Yang Xiaodong Wang Yongqiang Wang Jinhong Chen Yiyue Feng Xuemei Deng Yingmei Lu Xiaoling Hu Xiangxiang Li Juan Zhang Tao Shi Prof. Zhen Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(72):17289-17317
Sulfur-containing scaffold, as a ubiquitous structural motif, has been frequently used in natural products, bioactive chemicals and pharmaceuticals, particularly C−S/N−S bonds are indispensable in many biological important compounds and pharmaceuticals. Development of mild and general methods for C−S/N−S bonds formation has great significance in modern research. Iodine and its derivatives have been recognized as inexpensive, environmentally benign and easy-handled catalysts or reagents to promote the construction of C−S/N−S bonds under mild reaction conditions, with good regioselectivities and broad substrate scope. Especially based on this, several new strategies, such as oxidation relay strategy, have been greatly developed and accelerated the advancement of this field. This review focuses on recent advances in iodine and its derivatives promoted hybridized C−S/N−S bonds formation. The features and mechanisms of corresponding reactions are summarized and the results of some cases are compared with those of previous reports. In addition, the future of this domain is discussed. 相似文献
89.
Dr. Yongqi Yao Dr. Qifu Lin Dr. Wen Yang Prof. Dr. Weitao Yang Prof. Dr. Fenglong Gu Prof. Dr. Wei Guo Prof. Dr. Dingqiao Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(25):5607-5610
A cobalt(II)-catalyzed [4+2] annulation of picolinamides with alkynes via C−H bond activation has been developed. The operationally simple annulation reaction allows for the synthesis of acyl-substituted 1H-benzoquinoline bearing multiple aromatic rings (up to 96 % yield) without co-oxidant or other oxidation factors under mild conditions. Several control experiments were carried out. This practical [4+2] annulation provides an efficient route to access highly functionalized compounds. 相似文献
90.
Dr. Ruofei Cheng Prof. Dr. Zaozao Qiu Prof. Dr. Zuowei Xie 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(32):7212-7218
Iridium-catalyzed formal alkyne hydroboration with cage B−H of o-carborane has been achieved, leading to the controlled synthesis of a series of 3,6-[trans-(AlkCH=CH)]2-o-carboranes (Alk=alkyl), 3-cis-(ArCH=CH)-o-carboranes (Ar=aryl), and 3-cis-(ArCH=CH)-6-trans-(AlkCH=CH)-o-carboranes in high yields with excellent regio- and very good cis–trans selectivity. The most electron-deficient B(3,6)−H vertices favor oxidative addition on electron-rich metal centers, which is responsible for the regioselectivity. On the other hand, the configuration of the resultant olefinic units is dominated by alkyne substituents. Alkyl groups lead to a trans-configuration whereas bulky aryl substitutions result in cis-configuration. 相似文献