biostudies-literatureUnknown3(12)Li GThe rate constants <i>k</i>_H (<i>k</i>_D) have been determined at 27 °C for H· (D·) transfer from CpCr(CO)₃H(D) to the C=C bonds of various enamides. This process leads to the formation of α-amino radicals. Vinyl enamides with <i>N</i>-alkyl and <i>N</i>-phenyl substituents have proven to be good H· acceptors, with rate constants close to those of styrene and methyl methacrylate. A methyl substituent on the incipient radical site decreases <i>k</i>_H by a factor of 4; a methyl substituent on the carbon that will receive the H· decreases <i>k</i>_H by a factor of 380. The measured <i>k</i>_H values indicate that these α-amino radicals can be used for the cyclization of enamides to pyrrolidines. A vanadium hydride, HV(CO)<sub>4</sJACS Au3366-3373https://www.ebi.ac.uk/biostudies/studies/S-EPMC10751771biostudies-literatureKinetics of H· Transfer from CpCr(CO)₃H to Various Enamides: Application to Construction of Pyrrolidines.PMC10751771Li GQian JHong XShi SNorton JRXu GXLiu JRfalseKinetics of H· Transfer from CpCr(CO)₃H to Various Enamides: Application to Construction of Pyrrolidines.The rate constants <i>k</i>_H (<i>k</i>_D) have been determined at 27 °C for H· (D·) transfer from CpCr(CO)₃H(D) to the C=C bonds of various enamides. This process leads to the formation of α-amino radicals. Vinyl enamides with <i>N</i>-alkyl and <i>N</i>-phenyl substituents have proven to be good H· acceptors, with rate constants close to those of styrene and methyl methacrylate. A methyl substituent on the incipient radical site decreases <i>k</i>_H by a factor of 4; a methyl substituent on the carbon that will receive the H· decreases <i>k</i>_H by a factor of 380. The measured <i>k</i>_H values indicate that these α-amino radicals can be used for the cyclization of enamides to pyrrolidines. A vanadium hydride, HV(CO)<sub>4</s2023-01-01T00:00:00Z2023 Dec2025-04-21T15:06:06.686Z2025-04-21T15:06:06.686ZS-EPMC107517713815565610.1021/jacsau.3c00529