Chemistry

[ASAP] Low-valent Iridium Enables “Outer-Sphere” Radical–Radical Coupling in Photoinduced Asymmetric Allylic Alkylation

AI Insight

This study investigates an iridium-catalyzed photoinduced asymmetric allylic alkylation reaction in which a low-valent iridium complex facilitates an "outer-sphere" radical-radical coupling mechanism. The research demonstrates that the iridium catalyst operates through a distinct mechanistic pathway compared to traditional inner-sphere organometallic processes, enabling enantioselective carbon-carbon bond formation via the coupling of two radical intermediates. The findings provide mechanistic insight into how photoredox catalysis and transition metal catalysis can be merged to achieve stereocontrolled transformations.


Asymmetric allylic alkylation is a fundamental reaction in synthetic chemistry used to construct chiral building blocks for pharmaceuticals and complex natural products. Understanding and exploiting this outer-sphere radical mechanism could open new routes to enantioselective synthesis that are otherwise difficult to achieve with conventional catalytic approaches.


TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.6c06502

Source: [ASAP] Low-valent Iridium Enables “Outer-Sphere” Radical–Radical Coupling in Photoinduced Asymmetric Allylic Alkylation