Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104, United States.
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210023, China.
J Am Chem Soc. 2017 Jun 28;139(25):8710-8717. doi: 10.1021/jacs.7b04149. Epub 2017 Jun 14.
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 sp 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.
已经设计、合成并评价了双功能桥联试剂，其通过六元环刚性固定以实现高效的涉及乙烯基硅烷的[1,5]-Brook 重排反应。受约束的桥联试剂随后被用于第二代阴离子接力化学（ARC）中，以允许 sp 稳定碳负离子的烷基化和 Pd 介导的交叉偶联反应（CCR）。然后，我们采用密度泛函理论（DFT）计算来理解[1,4]-和[1,5]-乙烯基 Brook 重排反应的机理和反应性趋势，以了解所需铜试剂和底物几何形状的作用。
