Asymmetric Lewis Acid Catalyzed Electrochemical Alkylation

Abstract

Lewis‐acid catalysis and electrochemistry represent two powerful fields that have found widespread application in organic chemistry. Reported herein is an asymmetric electrosynthesis in combination with a chiral Ni catalyst leading to an intermolecular alkylation reaction in good yields with excellent enantioselectivities (up to 97 % ee). Mechanistic studies suggest that the Lewis‐acid‐bound radical intermediate from a single‐electron anodic oxidation selectively reacts with the benzylic radical species to generate the desired adducts.

Powering the Future: How Can Electrochemistry Make a Difference in Organic Synthesis?

“…80 Very recently, Ackermann developed palladaelectro-catalyzed C-H alkenylations with full enantioselectivity control, which enabled the assembly of structurally complex helicenes by a novel transient directing-group electrochemical strategy (Scheme 5C). 81 The merger of electrosynthesis and asymmetric catalysis features the unique future possibilities of chiral solvents, 82 chiral electolytes, 83 or chiral electrodes. 84 However, despite key advances in asymmetric electrocatalysis, 85,86 major challenges remain.…”

Nickel-catalyzed switchable asymmetric electrochemical functionalization of alkenes

“…Different from classical enolate chemistry, merging stereoselective Lewis acid catalysis with electrochemistry could provide anodic oxidation-triggered electrophilic keto radical based on a single electron transfer (SET) process, thus offering a unique opportunity to access modular structural complexity with predictable reactivity (Fig. 1A) (35)(36)(37)(38).…”

Recent Applications of Homogeneous Catalysis in Electrochemical Organic Synthesis

“…Figure 43. Rh-catalyzed electro-oxidative cross-couplingLater in 2019, Guo and co-workers reported a method for Ni-catalyzed asymmetric electrochemical alkylation via benzylic C-H bond functionalization (Figure44a) 155. The imidazole…”