Qi Liu1, Yu Chen2, Xiao Zhang2, K N Houk3, Yong Liang2, Amos B Smith1. 1. Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104, United States. 2. State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210023, China. 3. Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095, United States.
Abstract
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.
The design, synthen class="Chemical">sis, 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.
Authors: Lufeng Zou; Robert S Paton; Albert Eschenmoser; Timothy R Newhouse; Phil S Baran; K N Houk Journal: J Org Chem Date: 2013-03-22 Impact factor: 4.354
Authors: Minh H Nguyen; Masashi Imanishi; Taichi Kurogi; Xuemei Wan; Jane E Ishmael; Kerry L McPhail; Amos B Smith Journal: J Org Chem Date: 2018-02-26 Impact factor: 4.354