Zhang Guodong, Hu Zhiyong, Belitz Florian, Ou Yang, Pirkl Nico, Gooßen Lukas J
Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, Universitätsstr. 150, 44801, Bochum, Germany.
Angew Chem Int Ed Engl. 2019 May 6;58(19):6435-6439. doi: 10.1002/anie.201901309. Epub 2019 Apr 4.
In the presence of a [Cp*RhCl ] catalyst, the Lewis acid In(OTf) , and the mild base Na CO , aromatic carboxylates and α,β-unsaturated ketones undergo a unique hydroarylation/Claisen/retro-Claisen process to give the corresponding indanones. In this carboxylate-directed ortho-C-H annelation, the C-COR bond of the ketone and the CO-OH group of the aromatic carboxylate are cleaved, and the hydroxy group is transferred from the aromatic to the aliphatic acyl residue. This reactivity is synthetically useful, particularly when starting from cyclic ketones, which are converted into indanones bearing aliphatic carboxylate side chains, thus greatly increasing the molecular complexity of aromatic carboxylates in a single step.
在[Cp*RhCl]催化剂、路易斯酸In(OTf)₃和弱碱Na₂CO₃存在的情况下，芳香羧酸酯和α,β-不饱和酮会经历独特的氢芳基化/克莱森重排/逆克莱森重排过程，生成相应的茚满酮。在这种羧酸酯导向的邻位C-H环化反应中，酮的C-COR键和芳香羧酸酯的CO-OH基团会发生断裂，羟基从芳环转移至脂肪族酰基残基上。这种反应活性在合成上具有实用性，特别是从环状酮开始反应时，环状酮会转化为带有脂肪族羧酸酯侧链的茚满酮，从而在一步反应中极大地增加了芳香羧酸酯的分子复杂性。
