Tethering Three Radical Cascades for Controlled Termination of Radical Alkyne peri-Annulations: Making Phenalenyl Ketones without Oxidants.

Although Bu3Sn-mediated radical alkyne peri-annulations allow access to phenalenyl ring systems, the oxidative termination of these cascades provides only a limited selection of the possible isomeric phenalenone products with product selectivity controlled by the intrinsic properties of the new cyclic systems. In this work, we report an oxidant-free termination strategy that can overcome this limitation and enable selective access to the full set of isomerically functionalized phenalenones. The key to preferential termination is the preinstallation of a "weak link" that undergoes C-O fragmentation in the final cascade step. Breaking a C-O bond is assisted by entropy, gain of conjugation in the product, and release of stabilized radical fragments. This strategy is expanded to radical exo-dig cyclization cascades of oligoalkynes, which provide access to isomeric π-extended phenalenones. Conveniently, these cascades introduce functionalities (i.e., Bu3Sn and iodide moieties) amenable to further cross-coupling reactions. Consequently, a variety of polyaromatic diones, which could serve as phenalenyl-based open-shell precursors, can be synthesized.

Sex Doll Specifications versus Human Body Characteristics.

Sex dolls have been criticized for reproducing unrealistic expectations about human bodies. Yet precise sex doll measurements are lacking in the literature nor has there been any systematic attempt to determine the extent to which sex dolls exaggerate human characteristics. To address this gap, we compared the specifications of sex dolls marketed in the USA with the characteristics of women and men living in the USA. Specifically, we tested if and to what degree female dolls were slimmer (H1) and male dolls more muscular (H2) than female and male humans, respectively. Furthermore, we tested if and to what degree female dolls' breasts (H3) and male dolls' penises (H4) were larger than those of women and men. We also tested if sex dolls' observed race/ethnicity was more often White than that of the US population (H5). In 2023, we collected the measures of all 757 full-body sex dolls marketed by the US retailer SexyRealSexDolls.com. Body measures from the US population were extracted from scientific literature. Descriptive and inferential statistical analyses were performed using R. All hypotheses were fully or partially confirmed, which indicated that sex dolls marketed in the USA are not realistic depictions of the US population but hypergendered (H1, H2), hypersexualized (H3, H4), and racially fetishized (H5). Implications of the lack of realism are discussed.