Rhodium‐Catalyzed Annelation of Benzoic Acids with α,β‐Unsaturated Ketones with Cleavage of C−H, CO−OH, and C−C Bonds
作者:Guodong Zhang、Zhiyong Hu、Florian Belitz、Yang Ou、Nico Pirkl、Lukas J. Gooßen
DOI:10.1002/anie.201901309
日期:2019.5.6
In the presence of a [Cp*RhCl2]2 catalyst, the Lewis acid In(OTf)3, and the mild base Na2CO3, 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
在[Cp * RhCl 2 ] 2催化剂,路易斯酸In(OTf)3和弱碱Na 2 CO 3的存在下,芳族羧酸盐和α,β-不饱和酮经历独特的加氢芳基化/克莱森/复古克莱森工艺给予相应的茚满酮。在这个羧酸盐定向的邻位中‐C H脱环,酮的C-COR键和芳族羧酸的CO-OH基团被裂解,羟基从芳族基转移至脂肪族酰基残基。该反应性在合成上是有用的,特别是当从环状酮开始时,该环状酮被转化为带有脂肪族羧酸盐侧链的茚满酮,因此在一个步骤中大大增加了芳香族羧酸盐的分子复杂性。