Chemoselective Transformation of Diarylethanones to Arylmethanoic Acids and Diarylmethanones and Mechanistic Insights.
Chemoselective Transformation of Diarylethanones to Arylmethanoic Acids and Diarylmethanones and Mechanistic Insights.
复制标题
DOI：
10.1021/acs.joc.5b02506
复制
发表时间：
2016-01
期刊：
影响因子：
--
通讯作者：
Xing Wang;Rui-Xi Chen;Zengfeng Wei;Chen-Yang Zhang;Haiyang Tu;A. Zhang
中科院分区：
文献类型：
--
作者：
Xing Wang;Rui-Xi Chen;Zengfeng Wei;Chen-Yang Zhang;Haiyang Tu;A. Zhang
研究了二芳基乙烷酮通过好氧氧化裂解生成芳基甲烷酸或连续好氧氧化/苯甲酸重排/脱羧生成二芳基甲烷酮的化学选择性转化。这种转化是可控的，适用于广泛的基材，并提供良好到优异产量的所需产品。(1)H NMR跟踪和单晶x射线衍射揭示了一个复杂的机制网络，其中两个常见的中间体，α-酮氢过氧化物和二乙基乙二酮，提出并验证了三个可能的途径。这些途径是相互联系的，可以通过改变反应条件来合理地切换。这种方法可以大规模合成并获得许多有价值的化合物，包括维生素B3、二苯酸和非甾体抗炎药酮洛芬。目前的协议代表了在利用复杂的机制网络来控制反应途径方面向前迈出的一步，实现了从同一类起始材料的不同合成。
The chemoselective transformation of diarylethanones via either aerobic oxidative cleavage to give arylmethanoic acids or tandem aerobic oxidation/benzilic acid rearrangement/decarboxylation to give diarylmethanones has been developed. The transformation is controllable and applicable to a broad spectrum of substrates and affords the desired products in good to excellent yields. Mechanistic insights with control reactions, (1)H NMR tracking, and single-crystal X-ray diffraction reveal a complex mechanistic network in which two common intermediates, α-ketohydroperoxide and diarylethanedione, and three plausible pathways are proposed and verified. These pathways are interlinked and can be switched reasonably by changing the reaction conditions. This method enables scalable synthesis and access to a number of valuable compounds, including vitamin B3, diphenic acid, and the nonsteroidal anti-inflammatory drug ketoprofen. The present protocol represents a step forward in exploiting complex mechanistic networks to control reaction pathways, achieving divergent syntheses from the same class of starting materials.