Sulfur-arylation of sulfenamides is reported. This reaction proceeds via a Chan-Lam-type coupling with commercially abundant boronic acids to give sulfilimines. A broad scope was established with a variety of readily accessible aryl and alkyl sulfenamide and boronic acid inputs. Synthetic utility and functional group compatibility were further demonstrated through the direct late-stage introduction of sulfilimines into approved drugs. Derivatization of the sulfilimine products provided access to medicinally relevant sulfoximines and sulfondiimines.
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http://dx.doi.org/10.1021/acs.orglett.3c00779 | DOI Listing |
J Org Chem
January 2025
School of Pharmacy, Guangdong Pharmaceutical University, Guangzhou 510006, P. R. China.
In this study, a metal-free and efficient method for the synthesis of sulfilimines and -sulfanylanilines in high yields with excellent chemoselectivities from oxonium aryne precursors with sulfenamides has been developed. This method features mild reaction conditions, simple operations, a general substrate scope, and good tolerance of functional groups. In addition, scale-up synthesis, related applications, and preliminary mechanistic explorations were also investigated.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2024
Department of Chemistry, Yale University, 225 Prospect St., New Haven, CT 06520, USA.
A general one-pot approach to diverse N-acylsulfenamides from a common S-phenethylsulfenamide starting material is reported. This approach was demonstrated by C-S bond formation utilizing commercially abundant (hetero)aryl iodides and boronic acids to provide sulfilimine intermediates that undergo thermal elimination of styrene. In contrast, all prior approaches to N-acylsulfenamides rely on thiol inputs to introduce sulfenamide S-substituents.
View Article and Find Full Text PDFOrg Lett
June 2023
Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
Sulfur-(hetero)arylation of sulfenamides with commercially abundant (hetero)aryl iodides by Ullmann-type coupling with inexpensive copper(I) iodide as the catalyst is reported. A broad scope of reaction inputs was demonstrated, including both aryl and alkyl sulfenamides and highly sterically hindered aryl and 5- and 6-membered ring heteroaryl iodides. Relevant to many bioactive high oxidation state sulfur compounds, the (hetero)arylation of -methyl sulfenamides is reported, including for complex aryl iodides.
View Article and Find Full Text PDFOrg Lett
June 2023
Key Laboratory of Chemical Biology and Traditional Chinese Medicine (Ministry of Educational of China), Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China.
Sulfilimines are key intermediates to common motifs in medicines and agrochemicals. Typically, this class of compounds are prepared by imidation of thioethers, transition-metal-catalyzed or base-promoted sulfur alkylation and transition-metal-catalyzed sulfur arylation. Here, we report a practical and efficient base-mediated sulfur arylation reaction for the preparation of sulfilimines.
View Article and Find Full Text PDFOrg Lett
April 2023
Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
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