Towards Ideal Synthesis: Alkenylation of Aryl CH Bonds by a Fujiwara–Moritani Reaction

Abstract

An overview of recent progress in the Fujiwara-Moritani reaction, which is the palladium-catalyzed oxidative coupling of arenes with olefins to afford alkenyl arenes, is described. It is emphasized that regioselectivity on aryl ortho- or meta-CH activation could be controlled very well in the presence of Pd, Rh, or Ru catalysts with the assistance of various chelation groups on aromatic rings in this coupling reaction. Catalytic alkenylation of aryl CH bonds from simple arenes is also discussed, especially from electron-deficient arenes. These advanced protocols would not only make the Fujiwara-Moritani reaction more useful and applicable in organic synthesis but also light the way for the further development of the functionalization of normal CH bonds.

Towards Sustainable C−H Functionalization Reactions: The Emerging Role of Bio‐Based Reaction Media

“…[32] Another recent example of aC ÀHf unctionalization process conducted in GVL is the Pd/C-catalyzed oxidative alkenylation of aromatics, in this case acetanilides, also known as Fujiwara-Moritanio rd ehydrogenative Heck reaction (Scheme 4). [33,34] A preliminaryscreening of reaction conditions allowed to identify benzoquinone and ap olymer-bound para-toluenesulfonic acid as optimal oxidant anda cid additive, respectively.Aseries of unsubstituted and substituted, either with electron-withdrawing or electron-donatingg roups, acetanilides was reacted with electron-poor alkenes,a ffording the alkenylated products in good to excellent yields. The reactiono ccurred in all cases with high selectivity,g iving the mono-functionalized product in the ortho position to the acetamido directingg roup.…”

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).…”

Regioselective Direct C‐Alkenylation of Indoles

“…All over the years, this procedure has been progressively extended to heteroaromatic compounds including indoles,a nd other five-membered ring derivatives. [13] In the FM reaction, aC ÀHa ctivationo ft he indole ring is provided by electrophilic Pd II complexes according to the general mechanism portrayedi nS cheme 3f or the preparation of a3alkenylated indole. [14] Interaction of the indole with the metal complexg enerates an adduct 1 whichb ys ubsequentd eprotonation leads to palladated intermediate 2.…”