The (Et_4N)_2[Fe_4(SPh)_10] stimulated reaction of α-bromonaphthalene with pinacolone carbanion in DMSO leads to the formation of 1-(α-naphthyl)pinacolone. The reaction is suggested in terms of SRN1 mechanism of ar...The (Et_4N)_2[Fe_4(SPh)_10] stimulated reaction of α-bromonaphthalene with pinacolone carbanion in DMSO leads to the formation of 1-(α-naphthyl)pinacolone. The reaction is suggested in terms of SRN1 mechanism of aromatic nucleophillic substitution and has potential value in synthesis to obtain (-substituted naphthalene derivaties.展开更多
Cross-coupling reactions between aryl halides and thiolates or selenolates typically require transition metals,photocatalysts,strong bases,or/and malodorous thiols/selenols,with various mechanisms proposed.This study ...Cross-coupling reactions between aryl halides and thiolates or selenolates typically require transition metals,photocatalysts,strong bases,or/and malodorous thiols/selenols,with various mechanisms proposed.This study aims to leverage a new application of neutral ChB to address these challenges and enable a very simple photoinduced cross-electrophile C—S/Se coupling using readily available chalcogen electrophiles.Mechanistic investigations have revealed the important role of neutral ChB in facilitating single electron transfer processes,thereby enabling the generation of thiolates/selenolates from stable chalcogen electrophiles andα-aminoalkyl radicals,which possess the capability to abstract halogen atoms from aryl iodides.Moreover,the study provided support for the radical nucleophilic substitution mechanism.展开更多
Dibromobiphenyl reacted with cynomethyl anion in ammonia under irradiation to form nucleophilic bis-substituted product in high yield without substantial monosubstituted product. Quantum yields for the formations of b...Dibromobiphenyl reacted with cynomethyl anion in ammonia under irradiation to form nucleophilic bis-substituted product in high yield without substantial monosubstituted product. Quantum yields for the formations of bis- and monosubstituted products were found to be 85.6 and 2.3×10-6 respectively, while the corresponding pseudo-first-order rates were 6.9×10-3 and 5.2×10-10 mol.L-1.S-1. Block up the possible electron transfer of 4-brome-4'-cyanomethylbiphenylyl radical anion to 4-cyanometbyl-biphenylyl radical and bromine ion.展开更多
文摘The (Et_4N)_2[Fe_4(SPh)_10] stimulated reaction of α-bromonaphthalene with pinacolone carbanion in DMSO leads to the formation of 1-(α-naphthyl)pinacolone. The reaction is suggested in terms of SRN1 mechanism of aromatic nucleophillic substitution and has potential value in synthesis to obtain (-substituted naphthalene derivaties.
基金financial support from the National Natural Science Foundation of China(Nos.22173103,52063008)the Academic Talent Plan of Guizhou Normal University(No.Qian Shi Xin Miao[2021]27)the Fundamental Research Funds for the Central Universities and Beijing National Laboratory for Molecular Sciences(BNLMS2023014).
文摘Cross-coupling reactions between aryl halides and thiolates or selenolates typically require transition metals,photocatalysts,strong bases,or/and malodorous thiols/selenols,with various mechanisms proposed.This study aims to leverage a new application of neutral ChB to address these challenges and enable a very simple photoinduced cross-electrophile C—S/Se coupling using readily available chalcogen electrophiles.Mechanistic investigations have revealed the important role of neutral ChB in facilitating single electron transfer processes,thereby enabling the generation of thiolates/selenolates from stable chalcogen electrophiles andα-aminoalkyl radicals,which possess the capability to abstract halogen atoms from aryl iodides.Moreover,the study provided support for the radical nucleophilic substitution mechanism.
基金Project supported by the National Natural Science Foundation of China.
文摘Dibromobiphenyl reacted with cynomethyl anion in ammonia under irradiation to form nucleophilic bis-substituted product in high yield without substantial monosubstituted product. Quantum yields for the formations of bis- and monosubstituted products were found to be 85.6 and 2.3×10-6 respectively, while the corresponding pseudo-first-order rates were 6.9×10-3 and 5.2×10-10 mol.L-1.S-1. Block up the possible electron transfer of 4-brome-4'-cyanomethylbiphenylyl radical anion to 4-cyanometbyl-biphenylyl radical and bromine ion.
