Type II Anion Relay Chemistry: Conformational Constraints To Achieve Effective [1,5]-Vinyl Brook Rearrangements

The design, synthesis,
and evaluation of bifunctional linchpins,
conformationally anchored on six-membered rings to achieve efficient
[1,5]-Brook rearrangements involving vinyl silanes have been achieved.
The restrained linchpins were subsequently exploited in type II anion
relay chemistry (ARC) to permit both alkylations and Pd-mediated cross-coupling
reactions (CCR) of sp2 stabilized carbanions. DFT calculations
were then employed to understand the mechanism and reactivity trends
of [1,4]- and [1,5]-vinyl Brook rearrangements to provide insight
on the role of the required copper reagent and the substrate geometry.