Palladium‐Catalyzed Cross‐Dehydrogenative Functionalization of C(sp²)H Bonds

Abstract

The catalytic cross-dehydrogenative coupling (CDC) reaction has received intense attention in recent years. The attractive feature of this coupling process is the formation of a C-C bond from two C-H moieties under oxidative conditions. In this Focus Review, recent advances in the palladium-catalyzed CDC reactions of C(sp(2) )-H bond are summarized, with a focus on the period from 2011 to early 2013.

Synthetic Applications of Oxidative Aromatic Coupling—From Biphenols to Nanographenes

“…Most of the reported metal‐catalyzed or ‐mediated C−H/C−H dehydrogenative coupling reactions involve palladium as the catalyst metal. There are some reports on palladium‐catalyzed arylations by coupling an arene with another bearing an ortho directing group . In this context, Song, You, and co‐workers reported reactions of anilide derivatives with arenes, which were catalyzed by palladium(II) acetate in the presence of ammonium peroxodisulfate as the oxidant and TFA as the solvent (Figure ) .…”

“…There are some reports on palladiumcatalyzed arylations by coupling an arene with another bearing an ortho directing group. [100][101][102][103][104] In this context, Song,Y ou, and co-workers reported reactions of anilide derivatives with arenes,w hich were catalyzed by palladium-(II) acetate in the presence of ammonium peroxodisulfate as the oxidant and TFAa st he solvent (Figure 8). [116] Crosscoupled products such as 125-127 were obtained in yields ranging from 31 %to95%.Aclosely related reaction, namely the palladium(II)-catalyzed dehydrogenative coupling of arenes with indolines at C7, has also been reported (products 128;F igure 8).…”

A facile access for the C-N bond formation by transition metal-free oxidative coupling of benzylic C-H bonds and amides

“…Particularly, the amination of Csp 3 -H bonds has led to significant results since the discovery of metal nitrenoids insertion into the C-H bonds [10][11][12][13]. Various transition-metal complexes including rhodium [14][15][16][17], ruthenium [18][19][20], palladium [21][22][23][24][25], manganese [26][27][28], silver [29,30], gold [31], copper [32][33][34][35][36][37][38][39], cobalt [40][41][42] and iron [43,44] as catalysts or mediators are essential to the success of these aliphatic C-H amination reactions. Due to the presence of transition-metal impurities in the final products and/or the costly metal catalysts, a strategy involving metal-free protocol would be an attractive approach for introducing nitrogen functional groups.…”

Oxidative Alkenylation of Fused Bicyclic Heterocycles

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] The number of publications and books [16][17][18][19] in synthetic organic and medicinal chemistry has increased tremendously ( Figure 1) (fewer than 85 papers/year in 2000 and 2001 and more than 350 papers/year from 2014 to 2017). [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] The number of publications and books [16][17][18][19] in synthetic organic and medicinal chemistry has increased tremendously ( Figure 1) (fewer than 85 papers/year in 2000 and 2001 and more than 350 papers/year from 2014 to 2017).…”