New Ligand-Counterion System for Sustainable Ether Production

对于绿色化学解决方案和制药行业,以耐久的方式形成新的有机债券至关重要。目前,日记醚合成需要罕见的过渡金属催化剂或大量的有机溶剂。

可持续以太生产的新配体 - 触发系统。
Scientists use cooperative action of a ligand-counterion system for sustainable ether production necessary for pharmaceutical applications. Image Credit: Ritsumeikan University

In a new study, scientists fromRitsumeikan University在没有过渡金属催化剂的情况下,在水性环境中,在水性环境中获得了广泛的日记醚。这是迈向绿色有机化学未来的关键步骤。

药物的持续发展依赖于发展广泛的化学键的潜力。日记醚的特征是存在与两个芳基相关的氧原子,已知是一类由广泛应用组成的有机化合物。日记醚被认为是阻碍感染的制冷剂和防腐剂。

日记醚一直是研究兴趣的主题,因为事实证明它们的有机合成很困难。当第二种芳基被酒精氢取代时,它们可以由芳基酒精或苯酚开发。

然而,当前的苯酚O-酰化技术被认为是效率低下的,并利用了稀有的过渡金属催化剂(非常明显的是钯催化的交叉偶联反应赢得了2010年诺贝尔化学奖)。它们也是不可选择的,这意味着生产了几种不同的侧产品,从而降低了首选有机化合物的效率和最终产量。

Currently, a highly sustainable alternative to transition metal catalysts has been suggested by a research group from Ritsumeikan University, Japan. In this work, the transition metal has been replaced with a readily available and easily synthesized starting material, known as trimethoxyphenyl (TMP)-iodonium(III) acetate.

This iodonium salt contains two key structures, namely the TMP ligand and the acetate counterion, that work together to increase the reactivity of the O-arylation reaction and, in turn, enhance the ether bond formation, leading to significantly higher yields of diaryl ethers than has been reported in the past. It is a perfect teamwork

Kotaro Kikushima, Study Lead Author and Assistant Professor, Ritsumeikan University

该研究于3月18日发布th, 2022, in the journal有机信件

Depending on the structural features of phenyl (TMP)iodonium acetate, the scientists forecasted that the diaryliodonium salt would possess high reactivity. Consequently, the combination of the trimethoxyphenyl group and acetate anion collaborating to improve the reactivity of the phenol oxygen atom was identified initially in their study.

The range and diversity of compounds are considered crucial factors when developing methods for a green and sustainable chemistry future. For this method to be tested, the researchers analyzed and utilized several organic functional groups for O-arylation.

研究人员发现,与其他报道的方法相比,该技术对一系列功能组非常强大且耐受性,从而产生了广泛的醚,其产量要高得多,这是工业应用的重要考虑因素。

此外,通过以克规模执行反应,从而表明了将该过程扩展到工业需求的能力,从而保持了高效率。除了高产和可持续的起始材料外,该技术比现有方法更具额外的好处:选择性提高。欧洲杯足球竞彩

TMP组指示另一个功能组的选择性芳基化,从而实现了更多的控制,而无需不良的侧产品。

目前的方法将在绿色的可持续条件下为多种有用的有机分子提供一种具有成本效益且强大的访问,而无需过渡金属催化剂。

Toshifumi Dohi,研究合着者兼Ritsumeikan大学教授

Dohi stated, “Our next goal is to recycle and re-use the iodine-containing waste, which is formed as a side product during the arylation. Electrochemical or photochemical methods could then be used to sustainably restore the hypervalent iodine (III) which could then be used in another arylation。”

在提出的芳基反应中添加这种绿色回收计划将为有害化学废物中的无过渡金属键形成提供完美的可持续合成方法,这是有机合成可持续性的地震转变。

在说明的配体和柜台之间出色的团队合作的帮助下,有机化学的未来似乎从未如此绿色。

期刊参考:

Kikushima, K.,。((2022) Ligand- and Counterion-Assisted Phenol O-Arylation with TMP-Iodonium(III) Acetates.有机信件doi.org/10.1021/acs.orglett.2c00294

Source:http://en.ritsumei.ac.jp/

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