Organic Chemistry

Accessing Unusual Reactivity through Chelation-Promoted Bond Weakening



Highly reducing Sm(II) reductants and protic ligands were used as a platform to ascertain the relationship between low-valent metal-protic ligand affinity and degree of ligand X-H bond weakening with the goal of forming potent PCET reductants. Among the Sm(II)-protic ligand reductant systems investigated, the samarium dibromide N-methylethanolamine (SmBr2-NMEA) reagent system displayed the best combination of metal-ligand affinity and stability against H2 evolution. Use of SmBr2-NMEA afforded the reduction of a range of substrates that are typically recalcitrant to single electron reduction including alkynes, lactones, and arenes as stable as biphenyl. Moreover, the unique role of NMEA as a chelating ligand for Sm(II) was demonstrated by the reductive cyclization of unactivated esters bearing pendant olefins in contrast to the SmBr2-water-amine system. Finally, the SmBr2-NMEA reagent system was found to reduce substrates analogous to key intermediates in the nitrogen fixation process. These results reveal SmBr2-NMEA to be a powerful reductant for a wide range of challenging substrates and demonstrate the potential for the rational design of PCET reagents with exceptionally weak X-H bonds.


Thumbnail image of JACS SmBr2 NMEA (Final).pdf

Supplementary material

Thumbnail image of SmBr2 NMEA SI (Final).pdf
Accessing Unusual Reactivity through Chelation-Promoted Bond Weakening - SI
Supporting Information