2,2-Difluoroethylation of Heteroatom Nucleophiles via a Hypervalent Iodine Strategy.

The 2,2-difluoroethyl group is an important lipophilic hydrogen bond donor in medicinal chemistry, but its incorporation into small molecules is often challenging. Herein, we demonstrate electrophilic 2,2-difluoroethylation of thiol, amine and alcohol nucleophiles with a hypervalent iodine reagent, (2,2-difluoro-ethyl)(aryl)iodonium triflate, via a proposed ligand coupling mechanism. This transformation offers a complementary strategy to existing 2,2-difluoroethylation methods and allows access to a wide range of 2,2-difluoroethylated nucleophiles, including the drugs Captopril, Normorphine and Mefloquine.

Patterns of Sexual Harassment: An Intersectional Approach to Reported Victimization in a Campus Climate Survey of Students at Irish Higher Education Institutions.

This study explores how identifying with multiple minority groups relates to sexual harassment victimization (SHV) among students in higher education institutions in Ireland (n = 6,002). Results show that gender nonconforming and female students were more likely than males to experience SHV. Bisexual or queer and gay or lesbian students were more likely than their heterosexual peers to experience SHV. Students with a physical or cognitive disability were more likely to experience SHV than those who reported no disability, and white students were more likely than minority ethnic groups to experience SHV. When controlling for sexual orientation, gender, and disability status, students who identified as both gay and lesbian and reported a cognitive disability were 8.5 times more likely to experience SHV. Victims of SHV reported having lower scores on perceived institutional support items than those who had not experienced SHV.

Stereoselective two-carbon ring expansion of allylic amines via electronic control of palladium-promoted equilibria.

General methodologies enabling the two-carbon homologation of pyrrolidine and piperidine systems have yet to be developed. Herein we report that palladium-catalysed allylic amine rearrangements enable efficient two-carbon ring expansion of 2-alkenyl pyrrolidine and piperidines to their azepane and azocane counterparts. Conditions are mild, tolerant of a range of functional groups and the process can occur with high enantioretention. The products formed undergo a range of orthogonal transformations, making them ideal scaffolds for the creation of compound libraries.