Synthetic exploration of sulfinyl radicals using sulfinyl sulfones

Sulfinyl radicals – one of the fundamental classes of S-centered radicals – have eluded synthetic application in organic chemistry for over 60 years, despite their potential to assemble valuable sulfoxide compounds. Here we report the successful generation and use of sulfinyl radicals in a dual radical addition/radical coupling with unsaturated hydrocarbons, where readily-accessed sulfinyl sulfones serve as the sulfinyl radical precursor. The strategy provides an entry to a variety of previously inaccessible linear and cyclic disulfurized adducts in a single step, and demonstrates tolerance to an extensive range of hydrocarbons and functional groups. Experimental and theoretical mechanistic investigations suggest that these reactions proceed through sequential sulfonyl and sulfinyl radical addition.

Synthetic exploration of sulfinyl radicals using sulfinyl sulfones

Sulfinyl radicals – one of the fundamental classes of S-centered radicals – have eluded synthetic application in organic chemistry for over 60 years, despite their potential to assemble valuable sulfoxide compounds. Here we report the successful generation and use of sulfinyl radicals in a dual radical addition / radical coupling with unsaturated hydrocarbons, where readily-accessed sulfinyl sulfones serve as the sulfinyl radical precursor. The strategy provides an entry to a variety of previously inaccessible linear and cyclic disulfurized adducts in a single step, and demonstrates excellent tolerance to an extensive range of hydrocarbons and functional groups. Experimental and theoretical mechanistic investigations suggest that these reactions proceed through sequential sulfonyl and sulfinyl radical addition.

An Ozonolysis Based Method and Applications for the Non-lethal Modification of Insect Cuticular Hydrocarbons

Cuticular hydrocarbons (CHCs) are important, multi-function components of the insect epicuticle. In Drosophila spp., CHCs provide protection from desiccation and serve as semiochemicals for both intra- and interspecific communication. We developed a non-lethal method for the modification of Drosophila CHCs profiles through the exposure of live insects to a high dose of ozone gas (~45,000 ppm). Drosophila suzukii that were treated with ozone showed a 1.63-3.10 fold reduction in unsaturated hydrocarbons with these CHCs shown to regenerate over 108 h. Changes in CHCs were correlated with significantly reduced desiccation resistance in both male and female D. suzukii at one h after ozone treatment. Interestingly, individuals treated with ozone showed increased desiccation resistance in comparison to controls at 108 h after ozone treatment. The methodology reported in this paper provides a novel approach to investigate the biosynthesis and functions of CHCs during the lifespan of an insect.