亚稳醌类分子的活性调控与仿生催化反应

Reactivity Modulation of Labile Quinones and Biomimetic Catalytic Transformations

醌及其亚胺类化合物是高亲电性、去芳构化的经典合成子,然而受限于易聚合、易水解等稳定性问题,其制备以及合成应用存在诸多挑战.我们利用仿生催化氧化策略,以易得的酚类化合物为原料,发展了金属催化剂/绿色终端氧化剂组合的催化体系,实现了高活性亚稳醌类分子的原位生成与活性调控,丰富了基于醌中间体的[3+2]、[3+3]、[4+2]等多个环加成反应并实现了区域选择性和立体选择性调控.对我们小组在亚稳醌的活性调控和仿生催化反应方面的研究成果做阶段性小节.

Quinones and their imine counterparts constitute a class of highly electrophilic and dearomatized synthon.Their preparation and synthetic applications are challenged by limited stability due to the tendency of dimerization/polymerization and hydrolysis.By taking a biomimetic catalytic oxidation strategy,we have developed oxidation systems comprising metal catalysts and green terminal oxidants that realized in situ oxidation of phenols and reactivity modulation of labile quinone intermediates.This has led to the establishment of several[3+2],[3+3]and[4+2]cycloadditions and control of their regioselectivity and stereoselectivity.In this account,our recent advances in reactivity modulation of labile quinones/quinone imines and their biomimetic catalytic transformations are summarized.