Radical-mediated rearrangements: past, present, and future

Abstract

This Review summarizes the past to present achievements in radical-mediated rearrangements, and brings up the prospects that may inspire colleagues to develop more useful synthetic tools based on radical rearrangements.

Switchable Divergent Synthesis Using Photocatalysis

“…Simultaneously, the reaction setup must be rigorously designed for reproducibility. In particular, the structure of the reaction intermediates can be easily changed depending on the reaction temperature . At present, photoreactors that can precisely control the reaction temperature are not widely available, and consequently, the widespread use of such devices will greatly support the development of this field in the future …”

Regioselective Fluoroalkylphosphorylation of Unactivated Alkenes by Radical‐Mediated Alkoxyphosphine Rearrangement**

“…Rearrangement reactions, as one of the most significant organic transformations, have been widely applied to improve the synthetic efficiency and molecular complexity [1] . Among them, radical‐mediated remote rearrangements constitute an elegant strategy for regiospecific introduction of functional groups that are difficult to introduce by other means [1c–f] . By combining with the intermolecular radical addition onto olefins, this strategy enables regioselective difunctionalization of olefins by shifting functionalities with π bonds from the distal position of molecules to the medial carbon of terminal olefin through subsequent radical cyclization and β‐scission (Scheme 1Aa) [2] .…”

Combination of radical functional group migration (FGM) and hydrogen atom transfer (HAT)

“…Radical rearrangements, such as FGM, have received increasing attention as a result of their support of effective pathways for the reorganization of chemical bonds and transposition of functional groups [1]. In the process, a moiety can migrate from one atom to another by successive rapture of inert chemical bonds.…”