RuH-Catalyzed Synthesis of 1,3-Diaryl Ketones via Cross- Coupling of Aromatic Enones with Aromatic Aldehydes and Mechanistic Insights
RuH-Catalyzed Synthesis of 1,3-Diaryl Ketones via Cross- Coupling of Aromatic Enones with Aromatic Aldehydes and Mechanistic Insights
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RuH 催化芳香烯酮与芳香醛交叉偶联合成 1,3-二芳基酮及机理见解
DOI：
10.1002/adsc.202200765
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Ilhyong Ryu
中科院分区：
文献类型：
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作者：
Takashi Kuwahara;Takahide Fukuyama;Baptiste Picard;Ilhyong Ryu
RuHCl(CO)(PPh3)3‐催化烯基酮与醛的交叉偶联已扩展到1,3‐二芳基1,3‐二酮的合成。该反应已成功应用于选择性雌激素受体调节剂PPT（丙基吡唑三醇）的合成。对苯基乙烯酮与RuHCl(CO)(PPh3)3的化学计量反应进行了研究，发现β -钌酮PhCOCH2CH2RuCl(CO)(PPh3)2在释放1分子PPh3的情况下形成了一个五元钌环。观察到该钌环在pph3存在下的催化活性表明，它处于静息状态，与氧- π -烯丙基钌平衡，这是与醛底物的关键偶联伙伴。
RuHCl(CO)(PPh3)3‐catalyzed cross‐coupling of alkenyl ketones with aldehydes has been extended to the synthesis of 1,3‐diaryl 1,3‐diketones. The reaction has been successfully applied to the synthesis of PPT (propyl pyrazole triol), a selective estrogen receptor modulator compound. A study of the stoichiometric reaction of phenyl vinyl ketone with RuHCl(CO)(PPh3)3has revealed that the β‐ruthenium ketone PhCOCH2CH2RuCl(CO)(PPh3)2, a five‐membered ruthenacycle is formed with liberation of one molecule of PPh3. The observed catalytic activity of this ruthenacycle in the presence of PPh3suggests that it serves as a resting state, in equilibrium with an oxa‐π‐allyl ruthenium species, which is the key coupling partner with aldehyde substrates.