Cationic Pd(II)-Catalyzed Fujiwara−Moritani Reactions at Room Temperature in Water

Abstract

PdII-catalyzed Fujiwara-Moritani reactions can be carried out without external acid at room temperature, and in water as the only medium. A highly active cationic PdII catalyst, [Pd(MeCN)4](BF4)2, easily activates aromatic C-H bonds to produce electron-rich cinnamates in good yields.

A Practical Strategy for the Structural Diversification of Aliphatic Scaffolds through the Palladium‐Catalyzed Picolinamide‐Directed Remote Functionalization of Unactivated C(sp3)H Bonds

“…Precedent for the catalytic alkenylation of C(sp 3 ) À H bonds is scarce; in most examples, simple acrylate or monosubstituted vinyl halides have been used. [17] We were pleased to find that the alkenylation of 1 with various disubstituted cyclic vinyl iodides provided the desired alkenylated product in moderate to good yields at slightly elevated temperatures (vinyl iodide (1.5 equiv), Pd(OAc) 2 (0.1 equiv), and AgOAc (1.5 equiv) in tBuOH at 110 8C). Interestingly, the ring size of the cyclic vinyl iodide had a strong influence on the reaction yield; the seven-membered iodide gave the highest yield (69 % yield of the isolated product 34).…”

ChemInform Abstract: Designer‐Surfactant‐Enabled Cross‐Couplings in Water at Room Temperature

“…44 Alternatively, it has been shown that Fujiwara–Moritani coupling reactions with acrylates can be carried out in PTS–water (eq 12) 45 by using a cationic source of palladium, as in commercially available [Pd(MeCN) 4 ](BF 4 ) 2 , 46 Both benzoquinone (1 equiv) and AgNO 3 (2 equiv) are required. Double functionalization ortho to the amide directing group is not observed here as well.…”

Palladium Catalyzed C−C and C−N Bond Formation via ortho C−H Activation and Decarboxylative Strategy: A Practical Approach towards N‐Acylated Indoles

“…The Palladium is probably inserted at the alpha position of olefin (COOH attached carbon) which exclusively leads to 3-substituted indoles exhibiting high regioselectivity. [17] Based on the existing literature, [18][19][20][21] and isolation of product; a plausible mechanism involving palladium catalytic cycle is outlined in Figure 2. The reaction is assumed to proceed via ortho-palladation of the anilide 1 giving intermediates I and II in succession.…”