Year: 2025
Type: article
Abstract: Transition metal-catalyzed C–C reductive coupling reactions avoid the direct use of sensitive metal reagents, representing a practical approach for constructing the skeletons of organic compounds. However, such reactions face significant challenges in constructing quaternary carbon centers. Herein, we report an example of iron-catalyzed reductive cross-coupling reaction of tertiary alkyl halides with allyl halides by using phosphine ligands. A directing strategy is developed for diverse reductive couplings of 3o C(sp3) with 1o C(sp3) and even 2o C(sp3). The directing effect of the carbonyl of amides and esters facilitates the iron catalyst in overcoming the substantial steric hindrance and numerous competing side reactions, allowing the reaction to proceed smoothly. The current study develops a directing strategy for highly steric reductive coupling reactions, and offers new insights into the efficient construction of complex C(sp3)–C(sp3) bonds using iron catalysts modified with phosphine ligands. Iron-catalyzed C–C reductive coupling avoids sensitive reagents but struggles to build quaternary centers. Using phosphine-ligated Fe and carbonyl directing groups, this work enables tertiary–primary/secondary C(sp³) coupling under mild conditions.
Source: Nature Communications
Institution: Nankai University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $6,990
Awards: G2045810780, G2777012027, G3564631667
OpenAlex ID: W4415958222