Sobie Kristin M, Albritton Matthew, Yang Yinuo, Alves Mariana M, Roitberg Adrian, Grenning Alexander J
Department of Chemistry, University of Florida PO Box 117200 Gainesville FL 32611 USA
Chem Sci. 2022 Jan 21;13(7):1951-1956. doi: 10.1039/d1sc06307c. eCollection 2022 Feb 16.
Herein reported is a strategy for constructing vicinal 4°/3° carbons reductive Cope rearrangement. Substrates have been designed which exhibit Cope rearrangement kinetic barriers of ∼23 kcal mol with isoenergetic favorability (Δ ∼ 0). These fluxional/shape-shifting molecules can be driven forward by chemoselective reduction to useful polyfunctionalized building blocks.
本文报道了一种构建邻位4°/3°碳的还原Cope重排的策略。已设计出底物,其表现出约23千卡/摩尔的Cope重排动力学势垒,具有等能量优势(Δ~0)。这些具有动态变化/形状变化的分子可通过化学选择性还原驱动生成有用的多官能化结构单元。