Kong Fanji, Chen Shusen, Chen Junqi, Liu Chang, Zhu Weihao, Dickie Diane A, Schinski William L, Zhang Sen, Ess Daniel H, Gunnoe T Brent
Department of Chemistry, University of Virginia, Charlottesville, VA 22904, USA.
Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84604, USA.
Sci Adv. 2022 Aug 26;8(34):eadd1594. doi: 10.1126/sciadv.add1594. Epub 2022 Aug 24.
We report carbon-hydrogen acetoxylation of nondirected arenes benzene and toluene, as well as related functionalization with pivalate and 2-ethylhexanoate ester groups, using simple copper(II) [Cu(II)] salts with over 80% yield. By changing the ratio of benzene and Cu(II) salts, 2.4% conversion of benzene can be reached. Combined experimental and computational studies results indicate that the arene carbon-hydrogen functionalization likely occurs by a nonradical Cu(II)-mediated organometallic pathway. The Cu(II) salts used in the reaction can be isolated, recycled, and reused with little change in reactivity. In addition, the Cu(II) salts can be regenerated in situ using oxygen and, after the removal of the generated water, the arene carbon-hydrogen acetoxylation and related esterification reactions can be continued, which leads to a process that enables recycling of Cu(II).
我们报道了使用简单的铜（II）[Cu（II）]盐，对非定向芳烃苯和甲苯进行碳-氢乙酰氧基化反应，以及与新戊酸酯和2-乙基己酸酯基团的相关官能化反应，产率超过80%。通过改变苯与Cu（II）盐的比例，可实现苯2.4%的转化率。结合实验和计算研究结果表明，芳烃碳-氢官能化反应可能通过非自由基的Cu（II）介导的有机金属途径发生。反应中使用的Cu（II）盐可以分离、回收和再利用，其反应活性几乎没有变化。此外，Cu（II）盐可以利用氧气原位再生，在除去生成的水后，芳烃碳-氢乙酰氧基化反应和相关的酯化反应可以继续进行，这导致了一个能够循环利用Cu（II）的过程。
Zotero 插件
