Oxidative DMSO Cyclization Cascade to Bicyclic Hydroxyketonitriles

Abstract

Thermolysis of ω-iodoalkyl-β-siloxyalkenenitriles in DMSO triggers an oxidative cyclization cascade that affords highly oxygenated hydrindanones, decalones, and undecanones. The cyclization cascade is highly unusual on three counts: the cyclization installs a contiguous array of tertiary–quaternary–tertiary centers, thermolysis equilibrates a quaternary center, and the enolsilyl ether crossed-aldol proceeds without a catalyst.

DBDMH-Promoted Methylthiolation in DMSO: A Metal-Free Protocol to Methyl Sulfur Compounds with Multifunctional Groups

“…Dimethyl sulfoxide (DMSO) is widely used as a high-quality solvent because of its high solubility for many organic and inorganic compounds [22,23]. In addition to being used as a solvent, DMSO has also been used as a multifunctional, inexpensive and safe reagent as a carbon [24,25], sulfur [26,27] and oxygen source [28,29] in many reactions. However, due to the low activity of reaction substrates (especially for chlorides) or the fact that these reactions often require a higher temperature and a longer reaction time, the synthesis research progress in using DMSO as a sulfur source with halogen-containing compounds to construct molecules with the methyl sulfur group is relatively slow.…”