共查询到20条相似文献,搜索用时 15 毫秒
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《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(4):1121-1124
The first example of a hypervalent iodine(III)‐mediated oxidative fluorination of alkylsilanes by fluoride ions without the use of transition metals is demonstrated. This reaction is operationally simple, scalable, and proceeds under mild reaction conditions. Mechanistic studies suggest the involvement of a single‐electron transfer resulting from the interaction of an organopentafluorosilicate and aryliodonium difluoride, which were generated in situ from the corresponding alkylsilane and iodosobenzene, respectively, in the presence of fluoride ions. 相似文献
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Shin A. Moteki Asuka Usui Sermadurai Selvakumar Tiexin Zhang Keiji Maruoka 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(41):11240-11244
Direct acyl radical formation of linear aldehydes (RCH2‐CHO) and subsequent hydroacylation with electron‐deficient olefins can be effected with various types of metal and nonmetal catalysts/reagents. In marked contrast, however, no successful reports on the use of branched aldehydes have been made thus far because of their strong tendency of generating alkyl radicals through the facile decarbonylation of acyl radicals. Here, use of a hypervalent iodine(III) catalyst under visible light photolysis allows a mild way of generating acyl radicals from various branched aldehydes, thereby giving the corresponding hydroacylated products almost exclusively. Another characteristic feature of this approach is the catalytic use of hypervalent iodine(III) reagent, which is a rare example on the generation of radicals in hypervalent iodine chemistry. 相似文献
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Xiangdong Li Christopher Golz Manuel Alcarazo 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(28):9596-9600
The synthesis of 5‐(cyano)dibenzothiophenium triflate 9 , prepared by activation of dibenzo[b,d]thiophene‐5‐oxide with Tf2O and subsequent reaction with TMSCN is reported, and its reactivity as electrophilic cyanation reagent evaluated. The scalable preparation, easy handling and broad substrate scope of the electrophilic cyanation promoted by 9 , which includes amines, thiols, silyl enol ethers, alkenes, electron rich (hetero)arenes and polyaromatic hydrocarbons, illustrate the synthetic potential of this reagent. Importantly, Lewis acid activation of the reagent is not required for the transfer process. We additionally report herein biomimetic cyanocyclization cascade reactions, which are not promoted by typical electrophilic cyanation reagents, demonstrating the superior ability of 9 to trigger challenging transformations. 相似文献
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Michael M. Konnick Brian G. Hashiguchi Deepa Devarajan Nicholas C. Boaz T. Brent Gunnoe John T. Groves Niles Gunsalus Daniel H. Ess Roy A. Periana 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(39):10658-10662
Direct partial oxidation of methane, ethane, and propane to their respective trifluoroacetate esters is achieved by a homogeneous hypervalent iodine(III) complex in non‐superacidic (trifluoroacetic acid) solvent. The reaction is highly selective for ester formation (>99 %). In the case of ethane, greater than 0.5 M EtTFA can be achieved. Preliminary kinetic analysis and density functional calculations support a nonradical electrophilic CH activation and iodine alkyl functionalization mechanism. 相似文献
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《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(24):7098-7102
A new and efficient method for the synthesis of unsymmetrical 1,3‐butadiynes by gold‐catalyzed C(sp)–C(sp) cross‐coupling of terminal alkynes with alkynyl hypervalent iodine(III) reagents has been developed. The reaction features high selectivity and efficiency, mild reaction conditions, wide substrate scope, and functional‐group compatibility, and is a highly attractive complement to existing methods. Mechanistic studies reveal that formation of a phenanthrolinyl‐ligated gold(I) complex is crucial for the efficiency and selectivity of the target transformation. 相似文献
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Bo Xing Dr. Chuanfa Ni Prof. Dr. Jinbo Hu 《Angewandte Chemie (International ed. in English)》2018,57(31):9896-9900
An unprecedented hypervalent iodine(III) catalyzed Balz–Schiemann reaction is described. In the presence of a hypervalent iodine compound, the fluorination reaction proceeds under mild conditions (25–60 °C), and features a wide substrate scope and good functional‐group compatibility. 相似文献