01312nas a2200241 4500008004100000022001400041245008900055210006900144260000900213300001400222490000700236520051800243653000600761653002700767653001800794653002100812100002800833700001700861700002500878700002100903700002400924856012200948 2024 eng d a1359-734500aElectrochemically enabled (3+2) cycloaddition of unbiased alkenes and β-dicarbonyls0 aElectrochemically enabled 32 cycloaddition of unbiased alkenes a cMAY  a5836-58390 v603 a

A (3+2) cycloaddition between unbiased alkenes and 1,3-dicarbonyls is accomplished by judicious choice of electrode material and electrocatalyst to access dihydrofuran derivatives. A fluorinated porous carbon electrode with appropriate thickness governs unprecedented reactivity. This methodology eliminates the necessity for any stabilizing group within the alkene substrate. This is a rare example of the annulation of unbiased internal and terminal alkenes with cyclic and acyclic beta-dicarbonyls.

10a110a3-DICARBONYL COMPOUNDS10aDIHYDROFURANS10aFACILE SYNTHESIS1 aSuryawanshi, Sharad, M.1 aSahoo, Suman1 aShaligram, Parth, S.1 aManna, Narugopal1 aSamanta, Ramesh, C. uhttps://library.ncl.res.in/content/electrochemically-enabled-32-cycloaddition-unbiased-alkenes-and-%CE%B2-dicarbonyls02018nas 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

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 & 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 & 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.

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