- Freezing the conductance of platinum(II) complexes by quantum interference effect
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Understanding the impact of substituents on the quantum interference effect at single molecule scale is of great importance for the design of molecular devices. In this work, three platinum(II) complexes with –H, –NH2 and –NO2 groups on conductive backbones were designed and synthesized. Single-molecule conductance, which was measured using scanning tunnelling microscope break junction (STM-BJ) technique, demonstrated a conductance freeze phenomenon under the variation of substituents. Theoretical study revealed that, despite the electronic effect of the substituents shifting the energy level of molecular orbital, the quantum interference effect vanished the influence of electronic effect on the conductance and eventually leaded to the conductance freeze.
- Chen, Zhong-Ning,Pan, Zi-You,Wang, Jin-Yun,Yan, Sai-Sai,Zhang, Qian-Chong,Zheng, Da-Sheng
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supporting information
(2022/01/26)
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- Visible Light-Induced Metal-Free and Oxidant-Free Radical Cyclization of (2-Isocyanoaryl)(methyl)sulfanes with Ethers
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A novel cascade cyclization of (2-isocyanoaryl) (methyl)sulfanes and ethers is developed. With 4CzIPN as a photocatalyst and the irradiation of blue LED light, ether radicals are efficiently generated without adding any oxidant, endowing the strategy with features of oxidant-free, metal-free, mild reaction conditions, and operational simplicity. This strategy provides efficient approach to access various ether-containing benzothiazoles in acceptable to good yields.
- Xie, Xiao-Yu,Li, Yang,Xia, Yun-Tao,Luo, Kai,Wu, Lei
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supporting information
p. 4273 - 4277
(2021/06/14)
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- Sodium Sulfite-Involved Photocatalytic Radical Cascade Cyclization of 2-Isocyanoaryl Thioethers: Access to 2-CF2/CF3-Containing Benzothiazoles
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A visible-light-induced radical cascade cyclization of 2-isocyanoaryl thioethers for the synthesis of 2-CF2/CF3-containing benzothiazoles has been developed. Sodium sulfite can participate in the photocatalytic cycle as a reductant that efficiently transforms Ir4+ into Ir3+ to promote the fluoroalkylation under mild reaction conditions.
- Yuan, Yao,Dong, Wuheng,Gao, Xiaoshuang,Xie, Xiaomin,Zhang, Zhaoguo
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supporting information
p. 469 - 472
(2019/01/11)
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- Di- tert-butyl Peroxide-Mediated Radical C(sp2/sp3)-S Bond Cleavage and Group-Transfer Cyclization
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A novel strategy of cascade radical C(sp2/sp3)-S bond cleavage and group-transfer cyclization is disclosed. Triggered by alkyl radicals, varieties of 2-isocyanoaryl thioethers containing aliphatic, aryl, and heteroaromatic groups can be cleaved and precisely reinstalled to give benzothiazole derivatives. Mechanistic studies reveal that the cascade reaction undertakes an intermolecular pathway, and the inner radical sources (R radicals) exhibit high priority over those of methyl radical origin from di-tert-butyl peroxide.
- Luo, Kai,Yang, Wen-Chao,Wei, Kai,Liu, Yue,Wang, Jun-Ke,Wu, Lei
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supporting information
p. 7851 - 7856
(2019/10/11)
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- Dual role of ethyl bromodifluoroacetate in the formation of fluorine-containing heteroaromatic compounds
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An efficient one-pot cascade process via unprecedented quadruple cleavage of BrCF2COOEt with primary amines to afford valuable fluorine-containing heterocycles is described, in which BrCF2COOEt plays a dual role as a C1 synthon and a difluoroalkylating reagent for the first time. Mechanistic studies supported by DFT calculations suggest that a base plays an active role in the formation of the key intermediate isocyanides generated in situ from primary amines and difluorocarbene.
- Ma, Xingxing,Mai, Shaoyu,Zhou, Yao,Cheng, Gui-Juan,Song, Qiuling
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supporting information
p. 8960 - 8963
(2018/08/21)
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- Process for the preparation of N-(phenylethyl) anilines salts and solvates thereof useful as serotonin 5-HT6 antagonists
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The invention relates to a process for preparing N-(1-phenylethyl)anilines, salts, and solvates thereof, to novel intermediates, and to the use of the intermediates in the preparation of serotonin 5-HT6 antagonists.
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Page/Page column 49
(2009/10/01)
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- Formation of Sommelet-Hauser-Type Products, 2-Aminoarylmethyl Sulphides, and Nitrenium Ion Products, 2- and 4-Aminoaryl Sulphides, via an N-Arylazasulphonium Salt
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Reactions of a salt (1) formed at -60 deg C from trifluoroacetic anhydride and dimethyl sulphoxide (DMSO) with primary and secondary arylamines gave 2-aminoarylmethyl sulphides (6), (6') and (12) by a Sommelet-Hauser rearrangement of an ylide (5) formed by loss of a methyl proton of an N-arylazasulphonium salt (3) in the absence of base.The use of ethyl methyl sulphoxide instead of DMSO afforded a similar product (19b) by loss of not the ethyl but the methyl proton.However, the use of diethyl sulphoxide merely caused loss of an ethyl group from the N-arylazasulphonium salt to yield ethanesulphenanilide (20).The reaction of (1) with N-phenyl-1-naphthylamine gave mainly aminoaryl sulphides (13) and (14) via an arylnitrenium ion from the N-arylazasulphonium salt.In fact, the reaction of dimethyl sulphide (DMS) with arylnitrenium ions formed in the acid decomposition of aryl azides gave no Sommelet-Hauser-type products but 2- and 4-aminoaryl sulphides (22), (22') and (23).We also discuss the possibility of the N-arylazasulphonium salt being formed by reaction of the arylnitrenium ion with DMS.
- Takeuchi, Hiroshi,Itou, Kazuaki,Murai, Hirotaka,Koyama, Kikuhiko
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p. 3156 - 3188
(2007/10/02)
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