Competitive pathways in Pd-catalyzed synthesis of arylphenols

Modular Assembly of Spirocarbocyclic Scaffolds through Pd0‐Catalyzed Intermolecular Dearomatizing [2+2+1] Annulation of Bromonaphthols with Aryl Iodides and Alkynes

“…To address the aforementioned challenge, we commenced our studies with 1‐bromo‐2‐naphthol ( 2 a ), which possesses a higher potential to undergo dearomatization, as the bifunctional reactant II for the designed three‐component reaction (Table ). At the outset, a reaction mixture of 1 a , 2 a , and 3 a in DMF was heated at 100 °C in the presence of 5.0 mol % Pd(OAc) 2 , 12.0 mol % PPh 3 , 1.0 equivalent of NBE, and 2.0 equivalent of K 2 CO 3 , but neither the dearomatizing products ( V and VI ) nor dibenzofuran ( III ) were observed under these typical Catellani‐reaction conditions, and only side product 7 a was obtained through the annulation of 1 a with 3 a (entry 1). Upon optimization on the base, the envisioned 4 a was indeed obtained, albeit with low yields (entries 2–3).…”

Cis,exo-1,2,3,4,4a,13b-hexahydro-1,4-methano-5-isopropoxy-9H-tribenzo[b,f]azepine

“…Over the years, this palladium/norbornene-catalyzed C-H activation and functionalization reaction has been proven to be a powerful tool for the construction of complex molecules in a one-pot fashion [7,8]. In this context, we have successfully applied this methodology to the synthesis of many compounds, including natural product derivatives [9][10][11][12][13][14][15][16][17][18][19][20]. Notably, in 2011, we enriched the versatility of the Catellani reaction by the synthesis of dibenzo[b,f ]azepines [21].…”

Preparation of Secondary Phosphine Oxide Ligands through Nucleophilic Attack on Imines and Their Applications in Palladium‐Catalyzed Catellani Reactions

“…Nevertheless, the role played by conventional ligands such as phosphines remains doubtful in this type of reactions. Ever since the disclosure of the original Catellani reaction, there have been many interesting reports aimed at delving more deeply into the mechanism of this type of reactions and thereby improving the catalytic performances . As studies on SPO‐assisted Catellani‐type reactions are rare, it is of interest to us to explore the roles played by SPO‐type phosphine ligands in this type of reactions.…”