Tandem Remote Csp3-H Activation/Csp3-Csp3 Cleavage in Unstrained Aliphatic Chains Assisted by Palladium(II)

We report here a proof-of-concept for the cleavage of unstrained remote Csp(3)-Csp(3) bonds at room temperature assisted by a directing group, opening up new possibilities to use aliphatic carboxylic acids as suitable alkenyl coupling partners. This strategy involves the Pd-mediated Csp(3)-H activation directed by a tethered 8-aminoquinoline group, followed by a concerted asynchronous carbene insertion into the Pd-C bond, and an unexpected beta-carbon carbon bond splitting. The insertion of a coupling partner into a Pd-C bond is a novel route to promote C-C bond cleavage, which in contrast to most common methodologies does not rely on the use of strained carbocycles.