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Lactonization as a general route to beta-C(sp(3))-H functionalization 期刊论文
NATURE, 2020, 577 (7792) : 656-+
作者:  Washington, Harriet A.
收藏  |  浏览/下载:27/0  |  提交时间:2020/07/03

Functionalization of the beta-C-H bonds of aliphatic acids is emerging as a valuable synthetic disconnection that complements a wide range of conjugate addition reactions(1-5). Despite efforts for beta-C-H functionalization in carbon-carbon and carbon-heteroatom bond-forming reactions, these have numerous crucial limitations, especially for industrial-scale applications, including lack of mono-selectivity, use of expensive oxidants and limited scope(6-13). Notably, the majority of these reactions are incompatible with free aliphatic acids without exogenous directing groups. Considering the challenge of developing C-H activation reactions, it is not surprising that achieving different transformations requires independent catalyst design and directing group optimizations in each case. Here we report a Pd-catalysed beta-C(sp(3))-H lactonization of aliphatic acids enabled by a mono-N-protected beta-amino acid ligand. The highly strained and reactive beta-lactone products are versatile linchpins for the mono-selective installation of diverse alkyl, alkenyl, aryl, alkynyl, fluoro, hydroxyl and amino groups at the beta position of the parent acid, thus providing a route to many carboxylic acids. The use of inexpensive tert-butyl hydrogen peroxide as the oxidant to promote the desired selective reductive elimination from the Pd(IV) centre, as well as the ease of product purification without column chromatography, render this reaction amenable to tonne-scale manufacturing.


  
Gram-scale bottom-up flash graphene synthesis 期刊论文
NATURE, 2020, 577 (7792) : 647-651
作者:  Long, Haizhen;  Zhang, Liwei;  Lv, Mengjie;  Wen, Zengqi;  Zhang, Wenhao;  Chen, Xiulan;  Zhang, Peitao;  Li, Tongqing;  Chang, Luyuan;  Jin, Caiwei;  Wu, Guozhao;  Wang, Xi;  Yang, Fuquan;  Pei, Jianfeng;  Chen, Ping;  Margueron, Raphael;  Deng, Haiteng;  Zhu, Mingzhao;  Li, Guohong
收藏  |  浏览/下载:38/0  |  提交时间:2020/07/03

Most bulk-scale graphene is produced by a top-down approach, exfoliating graphite, which often requires large amounts of solvent with high-energy mixing, shearing, sonication or electrochemical treatment(1-3). Although chemical oxidation of graphite to graphene oxide promotes exfoliation, it requires harsh oxidants and leaves the graphene with a defective perforated structure after the subsequent reduction step(3,4). Bottom-up synthesis of high-quality graphene is often restricted to ultrasmall amounts if performed by chemical vapour deposition or advanced synthetic organic methods, or it provides a defect-ridden structure if carried out in bulk solution(4-6). Here we show that flash Joule heating of inexpensive carbon sources-such as coal, petroleum coke, biochar, carbon black, discarded food, rubber tyres and mixed plastic waste-can afford gram-scale quantities of graphene in less than one second. The product, named flash graphene (FG) after the process used to produce it, shows turbostratic arrangement (that is, little order) between the stacked graphene layers. FG synthesis uses no furnace and no solvents or reactive gases. Yields depend on the carbon content of the source  when using a high-carbon source, such as carbon black, anthracitic coal or calcined coke, yields can range from 80 to 90 per cent with carbon purity greater than 99 per cent. No purification steps are necessary. Raman spectroscopy analysis shows a low-intensity or absent D band for FG, indicating that FG has among the lowest defect concentrations reported so far for graphene, and confirms the turbostratic stacking of FG, which is clearly distinguished from turbostratic graphite. The disordered orientation of FG layers facilitates its rapid exfoliation upon mixing during composite formation. The electric energy cost for FG synthesis is only about 7.2 kilojoules per gram, which could render FG suitable for use in bulk composites of plastic, metals, plywood, concrete and other building materials.


Flash Joule heating of inexpensive carbon sources is used to produce gram-scale quantities of high-quality graphene in under a second, without the need for a furnace, solvents or reactive gases.


  
Act as NARSTO Management Coordinator and Conduct Research In Support of NARSTO Activities 科技报告
来源:US Department of Energy (DOE). 出版年: 2014
作者:  Pennell, William T.
收藏  |  浏览/下载:8/0  |  提交时间:2019/04/05
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