A vesicular self-assembled amphiphilic palladium NNC-pincer complex-catalyzed allylic arylation of allyl acetates with sodium tetraarylborates in water

Abstract

The authors would like to dedicate this article to Professor Jiro Tsuji for his peerless contribution to the broad discipline of organic chemistry Keywords:Allylic arylation Vesicle Palladium Pincer complex Catalysis Aqueous system a b s t r a c tThe allylic arylation of various allyl acetates with sodium tetraarylborates proceeded in water in the presence of a vesicular self-assembled amphiphilic palladium NNC-pincer complex to give the corresponding arylated products in high yield, whereas the same complex as an amorphous powder did not promote the reaction efficiently. The formation of a vesicular structure was therefore shown to be essential for efficient promotion of the reaction.

Recent Advances in Catalysis with Transition‐Metal Pincer Compounds

“…Besides the cross‐coupling reactions described above, pincer compounds have found applications in other, less‐common C−C coupling processes . Thus, Uozumi and co‐workers have recently reported a modified version of the Tsuji–Trost coupling in water; the catalyzed allylic arylation of allyl acetates is successfully achieved by using amphiphilic CNN–Pd pincer complex 89 a . The incorporation of both hydrophilic and hydrophobic functionalities into the structure of a palladium–pincer complex results in self‐assembly of the molecules in water, forming vesicles (Figure ).…”

π-Allylpalladium Complexes in Synthesis: An Update

“…Remarkably, the same complex as an amorphous powder did not efficiently catalyze the reaction, thus demonstrating that the formation of a vesicular structure was essential. 7 The directions of the hydrophilic and the hydrophobic chains attached to the phenanthroline ligand in the palladium complex seemed to influence the catalytic activity. The catalytic efficiency of Pd(II) aminoiminophosphoranate complexes 17 and 18 (Figure 1) in the Tsuji-Trost allylation reactions between diethyl malonate and allyl acetate have been reported by Kalsin, Vasil'ev and co-workers.…”

Synthesis of substituted allyl acetates from heterocyclic dienes by Pd-promoted arylation-acetoxylation cascade

“…[6][7][8][9][10][11][12][13] Amongst them, Pd-catalysed processes stand as the most intensively studied methodologies frequently used in the synthesis of various organic molecules, including naturally occurring substances. [14][15][16][17][18][19][20][21][22] The most common way to access allylic acetates utilizes allyl alcohols as starting materials, which are widely accessible via addition of vinyl-nucleophiles on aldehydes or ketones or simple nucleophilic additions on α,β-unsaturated equivalents. [23][24][25][26] Some alternative processes usually based on the acetoxylation of alkenes or related compounds have also been developed.…”