Organocatalyzed Birch Reduction Driven by Visible Light
Updated: Jul 28
The Birch reduction is a powerful synthetic methodology that uses solvated electrons to convert inert arenes to 1,4-cyclohexadienes—valuable intermediates for building molecular complexity. Birch reductions traditionally employ alkali metals dissolved in ammonia to produce a solvated electrons for the reduction of unactivated arenes such as benzene (Ered < -3.42 V vs. SCE). Photoredox catalysts have been gaining popularity in highly-reducing applications, but none have been reported to demonstrate reduction potentials powerful enough to reduce benzene. Here, we introduce benzo[ghi]perylene imides as new organic photoredox catalysts for Birch reductions performed at ambient temperature and driven by visible light from commercially available LEDs. Using low catalyst loadings (<1 mole percent), benzene and other functionalized arenes were selectively transformed to 1,4-cyclohexadienes in moderate to good yields in a completely metalfree reaction. Mechanistic studies support that this unprecedented visible light induced reactivity is enabled by the ability of the organic photoredox catalyst to harness the energy from two visible light photons to affect a single, high energy chemical transformation.
Reference: Cole, Justin; Chen, Dian-Feng; Kudisch, Max; Pearson, Ryan; Lim, Chern-Hooi; Miyake, Garret M., Organocatalyzed Birch Reduction Driven by Visible Light, J. Am. Chem. Soc. 2020
Date Published: July 14, 2020