α-Arylchalcogenation of acetone with diaryl dichalcogenide via metal-free oxidative C(sp3)–H bond functionalization

Recent Advances in Radical C–H Activation/Radical Cross-Coupling

“…A series of aliphatic and heterocyclic aromatic aldehydes were also found to be suitable for this transformation. Later, Wu and co-workers demonstrated a metal-free α-arylchalcogenation of acetone using diaryl dichalcogenides with a 2:1 mixture of TBHP and DTBP as the oxidant (Scheme b) . A range of diaryl disulfides were viable in this transformation, but only trace yields were obtained in the presence of nitro and amino substituents.…”

Carbon‐Sulfur Bond Constructions: From Transition‐Metal Catalysis to Sustainable Catalysis

“…Han, Pan and co-workers [30] have reported a DTBP promoted synthesis of 6-alkylthiophenanthridines 86 from disulfides 84 and 2-isocyanobiaryls 85 via thiolation of isocyanides and intramolecular radical aromatic cyclization process as shown in Path A, Scheme 25. Subsequently, a αarylthiolation of C(sp 3 )À H bond of acetone was also carried out by Yan et al [31] using a mixture of TBHP and DTBP as catalytic systems and disulfides as thiolation reagent as shown in Path B, Scheme 25. Zheng and co-workers [32] have developed NaI catalyzed acetamidosulphenylation process on A room temperature, K 2 S 2 O 8 /TFA catalyzed synthetic CÀ S bond forming protocol for the synthesis of unsymmetrical diaryl sulfide 93 using disulfide 91 and arenes 92 as coupling partners was developed by Kumar and co-workers [33] as shown in Path A, Scheme 26.…”

“…Han, Pan and co‐workers [30] have reported a DTBP promoted synthesis of 6‐alkylthiophenanthridines 86 from disulfides 84 and 2‐isocyanobiaryls 85 via thiolation of isocyanides and intramolecular radical aromatic cyclization process as shown in Path A, Scheme 25. Subsequently, a α‐arylthiolation of C(sp 3 )−H bond of acetone was also carried out by Yan et al [31] . using a mixture of TBHP and DTBP as catalytic systems and disulfides as thiolation reagent as shown in Path B, Scheme 25.…”

Electrochemical Oxidated-Iodide Promoted α-H Aryl(alkyl)selenation of Acetone for the Preparation of α-Aryl(alkyl)selenoacetones

“…1-苯硒基丙-2-酮(3a) [29] : 92%产率, 49.0 mg. 1 1-(4-甲基苯硒基)丙-2-酮(3b) [24] : 90%产率, 51.1 mg. 1-(4-甲氧基苯硒基)丙-2-酮(3c) [23] : 88%产率, 53.4 mg. 1 1-(4-氟苯硒基)丙-2-酮(3e) [23] : 84%产率, 48.5 mg. 1-(4-氯苯硒基)丙-2-酮(3f) [23] : 86%产率, 53.2 mg. 1 1-(4-溴苯硒基)丙-2-酮(3g) [23] : 87%产率, 63.5 mg.…”

“…电化学有机合 成策略在 C-H 官能团化 [40] 、C-C 键构建 [41][42] 以及 C-Z (N, P, S, Se)键 [43][44][45][46] 的构建方面显现出显著的优势. 根据上述控制实验结果以及已有文献报道 [23,43] , 提 出电化学促进丙酮芳(烷)硒化反应的两种可能机理 (Scheme 3). 路线 A: 首先, 碘离子在阳极表面失去电子 生成高氧化态的碘单质或碘鎓离子, 后者与二苯基二硒 醚反应得到苯硒基正离子(PhSe ＋ ), 苯硒基正离子与丙 酮反应得到目标产物和 H ＋ , 后者在阴极还原生成 H 2 ; 路线 B: 高氧化态的碘单质或碘鎓离子与丙酮反应得到 α-碘代丙酮, 后者与二苯基二硒醚反应获得目标产物.…”