Mechanistic Investigation, Wavelength-Dependent Reactivity, and Expanded Reactivity of <i>N</i>-Aryl Azacycle Photomediated Ring Contractions.

ABSTRACT: Under mild blue-light irradiation, α-acylated saturated heterocycles undergo a photomediated one-atom ring contraction that extrudes a heteroatom from the cyclic core. However, for nitrogenous heterocycles, this powerful skeletal edit has been limited to substrates bearing electron-withdrawing substituents on nitrogen. Moreover, the mechanism and wavelength-dependent efficiency of this transformation have remained unclear. In this work, we increased the electron richness of nitrogen in saturated azacycles to improve light absorption and strengthen critical intramolecular hydrogen bonding while enabling the direct installation of the photoreactive handle. As a result, a broadly expanded substrate scope, including underexplored electron-rich substrates and previously unsuccessful heterocycle

SUBMITTER: Kim SF 

PROVIDER: S-EPMC11646679 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature