Circumventing Mukaiyama oxidation: selective S–O bond formation via sulfenamide–alcohol coupling

• Guoling Huang,
• Huarui Zhu,
• Shuting Zhou,
• Wanlin Zheng,
• Fangpeng Liang,
• Zhibo Zhao,
• Yifei Chen and
• Xunbo Lu

Beilstein J. Org. Chem. 2026, 22, 158–166, doi:10.3762/bjoc.22.9

• /bjoc.22.9 Abstract A selective and efficient method for the synthesis of sulfinimidate esters via an NBS-promoted oxidative coupling of sulfenamides with alcohols has been developed. This operationally simple, metal-free protocol uses inexpensive and readily available reagents, operates under mild

• versatile intermediates for enantioselective S–C bond formation under mild and metal-free conditions. Keywords: asymmetric synthesis; late-stage functionalization; selective oxidation; sulfenamides; sulfinimidate esters; Introduction Sulfur is a privileged heteroatom in organic chemistry, celebrated for

• preparation of sulfinimidate esters remain scarce. For instance, Degennaro and Luisi reported a direct amination strategy using N,N’-disubstituted sulfenamides in alcoholic solvents; however, this method suffered from limited substrate scope [13]. Subsequently, Malacria and co-workers reported an oxidative

Dioxazolones as electrophilic amide sources in copper-catalyzed and -mediated transformations

• Seungmin Lee,
• Minsuk Kim,
• Hyewon Han and
• Jongwoo Son

Beilstein J. Org. Chem. 2025, 21, 200–216, doi:10.3762/bjoc.21.12

• to yield the stable intermediate INT-21. This intermediate releases the N-acyl iminophosphorane 16 through the incorporation of another organic phosphine, thereby regenerating the active copper species 17. 1.6 Synthesis of N-sulfenamides In 2022, the research groups of Wang and Chen introduced a

• modular copper-catalyzed method for the synthesis of N-acyl sulfenamides 20 from dioxazolones 18 using thiols 19 via nitrogen–sulfur bond formation (Scheme 7) [92]. Secondary and tertiary thiols were highly effective in affording the corresponding N-acyl sulfenamides 20a–d. Moreover, the bioactive motifs

• on both thiols and dioxazolones were well tolerated in late-stage functionalizations, representing excellent chemoselectivity (20e–g). This copper-catalyzed conjugative strategy allows for the modular preparation of biologically relevant N-acyl sulfenamides. Based on several mechanistic experiments

Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts

• Ritu Mamgain,
• Kokila Sakthivel and
• Fateh V. Singh

Beilstein J. Org. Chem. 2024, 20, 2891–2920, doi:10.3762/bjoc.20.243

• can present limitations. However, a more efficient method for synthesizing sulfilimines emerged in 2023, involving the selective S-arylation of sulfenamides 97 with diaryliodonium salts 98 at ambient temperature in the presence of air (Scheme 39). These innovative approaches offer promising

• on N-sulfenamides 97. Both, the divalent N-centered anion intermediate I and S-centered anionic intermediate II are the resonating structures which further react with the diaryliodonium salt to obtain intermediate III along with the elimination of triflate. Finally, intermediate III undergoes

N-Sulfenylsuccinimide/phthalimide: an alternative sulfenylating reagent in organic transformations

• Fatemeh Doraghi,
• Seyedeh Pegah Aledavoud,
• Mehdi Ghanbarlou,
• Bagher Larijani and
• Mohammad Mahdavi

Beilstein J. Org. Chem. 2023, 19, 1471–1502, doi:10.3762/bjoc.19.106

• -thiophthalimides led to sulfenamides promoted by 2-ethoxyethanol under microwave irradiation [100]. Alkylamines, such as morpholine, cyclohexylamine, pyrrolidine, and tert-butylamine were participated in this coupling process. All reactions occurred in a shorter time with higher chemical yields compared to the

Appel-reagent-mediated transformation of glycosyl hemiacetal derivatives into thioglycosides and glycosyl thiols

• Tamashree Ghosh,
• Abhishek Santra and
• Anup Kumar Misra

Beilstein J. Org. Chem. 2013, 9, 974–982, doi:10.3762/bjoc.9.112

• preparation of several glycosyl donors such as thioglycosides [33][34], glycosyl sulfenamides [35] and sulfonamides [36], glycosyl disulfides [37], glycosyl thionolactones [38], etc. A number of reports are available for the preparation of glycosyl thiols, which include (a) a two-step reaction of glycosyl

Synthesis of sulfonimidamides from sulfinamides by oxidation with N-chlorosuccinimide

• Olga García Mancheño and
• Carsten Bolm

Beilstein J. Org. Chem. 2007, 3, No. 25, doi:10.1186/1860-5397-3-25

• dialkylamino succinimidosulfonium salts from sulfenamides,[23] this non-explosive and easy to handle oxidizing agent was tested next. To our delight, 1a and NCS reacted well, and in combination with TsNHNa in acetonitrile sulfonimidamide 3a was obtained in excellent yield (94%, Table 1, Entry 12). Noteworthy