Rhodium‐Catalyzed ortho Acylation of Aromatic Carboxylic Acids

Acylation of (Hetero)Arenes through CH Activation with Aroyl Surrogates

“…Acid anhydrides, preformed or generated in situ, as a class of bulk chemicals were also found to be applicable as acyl sources. In 2013, Gooßen and co‐workers reported the rhodium‐catalyzed acylation of aromatic carboxylic acids 67. Good yields of the acylated products were obtained (Scheme ).…”

One‐Pot Synthesis of 3‐Alkylidenephthalides from Benzoic Acids by a Rhodium‐Catalyzed ortho‐CH Acylation Process

“…In the context of our research on catalytic reactions starting from benzoic acid substrates,20 we have developed a Rh‐catalyzed ortho ‐acylation of benzoic acids 16h. While optimizing the reaction conditions, we had occasionally detected trace quantities of 3‐alkylidenephthalides ( 3 ), and reasoned that they must have formed by acylalization and consecutive elimination of the cyclized isomer ( 4′ ) of the 2‐acylbenzoic acid products, as illustrated in the Scheme in Table 1.…”

Rhodium‐Catalyzed C(sp2)‐ or C(sp3)−H Bond Functionalization Assisted by Removable Directing Groups

“…[122] Av ariety of alkene coupling partners, including styrene derivatives, a,b-unsaturated carbonyl compounds,and even unactivated alkenes can also be used in the reaction (Scheme 27). [123][124][125][126][127] However,t he major drawback of free carboxylic acid directed CÀHf unctionalization is the uncontrolled reactivity,b ecause undesired decarboxylation often proceeds in such functionalized molecules. Ther eaction appears to proceed through the formation of ar hodium carbene intermediate,w hich is eventually generated from an alkene.…”