Access to distal meta-C–H functionalization of arylmethanesulfonic acid derivatives

Abstract

Herein, we report the meta-CH olefination of arylmethanesulfonates aided by a potentially versatile aliphatic nitrile-directing group under microwave irradiation conditions with fair to very good yields and good to outstanding...

Palladium catalyzed remote-meta-C–H functionalization of aniline scaffolds

“…), palladium acetate (10 mol%), N -acetyl glycine (40 mol%), silver acetate (2 equiv. ), HFIP (1.5 mL) at 90 °C for 25 minutes” under microwave irradiation in accordance with our previously reported procedure 37 (Scheme 2). Nevertheless, using T 1 as the directing template, the meta -regioselectivity of the corresponding product 3oa was determined to be “ m : others = 80 : 20” based on 1 H NMR analysis.…”

“…Our group is also active in investigating the C-H functionalization at meta-positions of an aromatic molecule with the help of different nitrile-containing templates. [33][34][35][36][37] On the other hand, anilines are privileged structural motifs prevalent in biologically relevant compounds; thus, there is great interest in the synthetic transformations of anilines to accomplish their functionalized derivatives. There are a plethora of reports on achieving functionalization at the ortho-position of anilines via electrophilic and auxiliary assisted ortho-C-H activation.…”

“…7–32 Our group is also active in investigating the C–H functionalization at meta -positions of an aromatic molecule with the help of different nitrile-containing templates. 33–37…”

Distal-C–H Functionalization of Biphenyl Scaffolds Assisted by Easily Removable/Recyclable Aliphatic Nitrile Templates

“…In this regard, a seminal study of the application of an end-on nitrile directing group for meta -selective C–H functionalization was reported by Yu et al in 2012 . As a result, numerous research teams have investigated a range of approaches using diverse “directing groups”. − Our lab has also been actively working on creating distal- m -C–H activation techniques recently, employing distinct directing groups; this could allow the m -C–H functionalization of aromatic scaffolds through the use of essentially straightforward and detachable aliphatic/aromatic nitrile templates. − These findings encouraged us to believe that the biphenyl scaffolds would enable remote meta -selective C–H olefination.…”