Meta-Selective C–H Functionalization of Arylsilanes Using a Silicon Tethered Directing Group

Abstract

We describe meta-selective C–H functionalization of arylsilanes using a Si-tethered directing group. The current method enables a selective alkenylation of arenes bearing a variety of functional groups, and several electron-deficient olefins are also applicable as coupling partners. Further functional group transformations of the silicon-tethered directing group provide multisubstituted arenes efficiently.

The Renaissance of Organo Nitriles in Organic Synthesis

“…Very recently in 2022, the Lee group reported a Pd(II)catalyzed synthesis of meta-CÀ H alkenylated arenes (28) by coupling arenes (26) and electron-deficient olefins (27) through a Si-tethered nitrile containing directing group T 5 (Scheme 11). [13] The method applies to a wide range of substrates, and further functional group transformations of the protecting group provide multi-substituted arenes.…”

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

“…6 This groundbreaking discovery opened the doors to site-selective functionalization of aromatic compounds through a diverse design of ligating group templates in the past decade. 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.…”