Ruthenium‐Catalyzed Monoalkenylation of Aromatic Ketones by Cleavage of Carbon–Heteroatom Bonds with Unconventional Chemoselectivity

Abstract

Ruthenium-catalyzed selective monoalkenylation of ortho C-O or C-N bonds of aromatic ketones was achieved. The reaction allowed the direct comparison of the relative reactivities of the cleavage of different carbon-heteroatom bonds, thus suggesting an unconventional chemoselectivity, where smaller, more-electron-donating groups are more easily cleaved. Selective monofunctionalization of C-O bonds in the presence of ortho C-H bonds was also achieved.

Ethereal C–O Bond Cleavage Mediated by Ni(0)-Ate Complex: A DFT Study

“…However, this breakthrough was overlooked for decades, until quite recently. After the development of improved conditions, ArOR can now be used as a coupling partner in several types of transition metal (TM)-catalyzed cross-couplings and related transformations, such as Suzuki-Miyaura-type (B), [24][25][26][27][28][29][30][31] Negishi-type (Zn or Al), [32][33][34][35][36] Murahashi-type (Li), [37][38][39][40] and other reactions. [41][42][43][44][45][46][47][48][49][50] As a continuation of our work in this area, we reported in 2012 the first ethereal Negishi-type coupling of aryl alkyl ether 36) (Chart 1(1)) and in 2016 we reported a systematic examination of ethereal Murahashi-type reaction 37) (Chart 1(2)).…”

Mild sp2Carbon–Oxygen Bond Activation by an Isolable Ruthenium(II) Bis(dinitrogen) Complex: Experiment and Theory

“…Oxidative addition of C–O bonds of ethers to Ru(0) carbonyl complexes has been widely invoked in Ru-catalyzed cross-coupling reactions of ethers with boronic esters. 18 − 22 Lin and co-workers have recently calculated a low-energy transition state for the oxidative addition of a C–O bond to the square-planar 16-electron complex trans- [Ru(PPh 3 ) 2 (CO)(L)]. 24 Directing-group-assisted C–H activation has been calculated to occur by similarly facile Ru(0)/Ru(II) redox process.…”

Efficient synthesis of 3,6,13,16-tetrasubstituted-tetrabenzo[a,d,j,m]coronenes by selective C–H/C–O arylations of anthraquinone derivatives

“…We have been working on the efficient syntheses of PAH derivatives based on the ruthenium-catalyzed C-H/C-O arylation reactions developed in our group [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33]. In the presence of ruthenium carbonyl phosphine complexes, the reaction of aromatic ketones possessing C-H bonds or C-OR (R = alkyl) bonds with arylboronates provided C-H or C-O arylation products [21][22][23][24][25][26][27][28][29][30][31][32][33]. Anthraquinone was chosen as a convenient template for the PAH syntheses, because various anthraquinone derivatives possessing zero to four oxygen substituents at the orthopositions are readily available and the regioselective arylation at the positions of either C-H or C-O bonds provided a variety of multiarylated anthraquinone derivatives [16][17][18][19][20].…”