Substituted six-membered cyclic hydrocarbons are common constituents of biologically active compounds. Although methods for the synthesis of thermodynamically favored, disubstituted cyclohexanes are well established, a reliable and modular protocol for the synthesis of their stereoisomers is still elusive. Herein, we report a general strategy for the modular synthesis of disubstituted cyclohexanes with excellent kinetic stereocontrol from readily accessible substituted methylenecyclohexanes by the implementation of chain-walking catalysis. Mechanistically, the initial introduction of a sterically demanding boron ester group adjacent to the cyclohexane is key to guiding the stereochemical outcome. The synthetic potential of this methodology has been highlighted in late-stage modification of complex bioactive molecules and in comparison with current cross-coupling techniques.

The construction of five and six membered heterocycle fused spirooxindoles was achieved via the [4 + 1] and formal [4 + 2] cycloadditions between our rationally designed four-membered synthons and pyridinium methylides and α-bromoacetophenones, respectively.

The hydride transfer enabled the first success of the regioselective dearomatization of indoles in the carbocyclic ring and the pyrrol ring, which was induced by ortho-quinone methides and vinylogous iminium...