02018nas a2200217   4500008004100000022001400041245012900055210006900184260000800253490000800261520122400269653002201493653001601515653002301531653001901554653002701573100002801600700001801628700002401646856013001670       2026                        eng d  a0018-019X00aElectrochemical generation of N-centered radicals and their reactivity toward cyclization and subsequent C―C bond cleavage0 aElectrochemical generation of Ncentered radicals and their react  cAPR0 v1093 a<p>
	N-containing heterocycles are widely used in medicinal chemistry, and they can be synthesized efficiently by the intramolecular cyclization of N-centered radicals. Furthermore, N-centered radicals also act as excellent hydrogen atom transfer (HAT) reagents. On the other hand, nitrogen atoms in the nitrogen-containing heterocycles are used as a handle to cleave stable five and six-membered rings. However, the electrochemical generation of N-centered radicals and their application in forming heterocycles have been extensively studied. Study beyond cyclization remains largely unexplored; in this manuscript, we summarize our new findings as follows. Under electrochemical conditions, the N &amp; horbar;H bond is cleaved, forming an N-centered radical that adds to the double bond in a 6-endo-trig cyclization fashion. The newly formed C-centered radical reacts with oxygen and undergoes C &amp; horbar;C bond cleavage to form the corresponding carbonyl compounds. The reactivity is dependent on the substituents present on nitrogen. In the case of aromatic amine-derived amide, the TEMPO trapping cyclization product was isolated. A mechanism has been proposed to explain the formation of the products.</p>
10aC-C bond cleavage10acyclization10aN-centered radical10aN-heterocycles10aoxidative ring opening1 aSuryawanshi, Sharad, M.1 aSingh, Mayuri1 aSamanta, Ramesh, C.  uhttps://library.ncl.res.in/content/electrochemical-generation-n-centered-radicals-and-their-reactivity-toward-cyclization-and