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Mechanistic Vistas of Trivalent Nitrogen Compound Reduction by Samarium Diiodide
Author(s) -
Maity Sandeepan,
Hoz Shmaryahu
Publication year - 2021
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202001438
Subject(s) - chemistry , lone pair , iodide , samarium diiodide , catalysis , azobenzene , nitrogen , samarium , photochemistry , surface modification , medicinal chemistry , combinatorial chemistry , organic chemistry , molecule
In trivalent nitrogen compounds, the nitrogen lone pair is highly amenable to bind to samarium iodide prior to electron transfer. As SmI 2 is more azaphilic than oxophilic, its affinity to the nitrogen lone pair is more pronounced in aza substrates than in the analogous carbonyl compounds. The impact of this binding is very large in terms of reaction rate and at the same time gives rise to unique mechanistic phenomena, which include unusual kinetic rate orders, catalysis by quantum dots, and remote functionalization. Even reduction of nitriles was found to be affected by this coordination to SmI 2 . This review focuses on the reduction mechanisms of three groups of compounds: imines, azobenzene, and nitriles.