A General Procedure for the Construction of 2‑Alkyl-Substituted Vinyl Sulfonyl Fluoride

A series of compact and multifunctional 2-alkyl-substituted vinyl sulfonyl fluorides were efficiently prepared from the corresponding alkyl iodides and 2-chloroprop-2-ene-1-sulfonyl fluoride (CESF). This Giese-type radical approach provided new and general access to alkenyl sulfonyl fluorides, including structures that would otherwise be challenging to synthesize with previously established methods. A correspondingly large collection of derivatization reactions was also demonstrated on the alkenyl sulfonyl fluorides

A Rh-Catalyzed Air and Moisture Tolerable Aldehyde (Ketone)-Directed Fluorosulfonylvinylation of Aryl C(<i>sp</i>²)–H Bonds

The first Rh-catalyzed activation of <i>ortho sp</i>² C–H bonds of aldehydes (ketones) for monoselective coupling with ethenesulfonyl fluoride was accomplished without covalent or transient preinstallation of imines. The 42 examples revealed that the developed method has the advantage of a wide scope and functional-group tolerability. Application of this method for complicated natural product modification was also accomplished

A Metal-Free Diverse Synthesis of Difluoromethylthioethers and Difluorobis(arylthio)methanes from RSX (X = SR, Cl, SO₂Ph) and TMSCF₂H

Construction of difluoromethylthioethers (<b>2</b>) and difluorobis­(arylthio)­methanes (<b>3</b>) from RSX (X = SR, Cl, SO₂Ph) and TMSCF₂H in the absence of transition metals has been explored. The reaction is dramatically influenced by the nature of the base and the molar ratio of the reactants. Reactions between RSX and TMSCF₂H in the presence of CsF provided <b>2</b> in good yields, whereas the reaction of RSX with TMSCF₂H in the presence of <i>t</i>-BuOK afforded <b>3</b> in good yields. These protocols allow for convenient and efficient access to both difluoromethylthioethers and difluorobis­(arylthio)­methanes

Synthesis of α,β-Unsaturated Carbonyl-Based Compounds, Oxime and Oxime Ether Analogs as Potential Anticancer Agents for Overcoming Cancer Multidrug Resistance by Modulation of Efflux Pumps in Tumor Cells

Sixty-nine novel α,β-unsaturated carbonyl based compounds, including cyclohexanone, tetralone, oxime, and oxime ether analogs, were synthesized. The antiproliferative activity determined by using seven different human cancer cell lines provided a structure–activity relationship. Compound <b>8ag</b> exhibited high antiproliferative activity against Panc-1, PaCa-2, A-549, and PC-3 cell lines, with IC₅₀ value of 0.02 μM, comparable to the positive control Erlotinib. The ten most active antiproliferative compounds were assessed for mechanistic effects on BRAF^V600E, EGFR TK kinases, and tubulin polymerization, and were investigated <i>in vitro</i> to reverse efflux-mediated resistance developed by cancer cells. Compound <b>8af</b> exhibited the most potent BRAF^V600E inhibitory activity with an IC₅₀ value of 0.9 μM. Oxime analog <b>7o</b> displayed the most potent EGFR TK inhibitory activity with an IC₅₀ of 0.07 μM, which was analogous to the positive control. Some analogs including <b>7f</b>, <b>8af</b>, and <b>8ag</b> showed a dual role as anticancer and MDR reversal agents