Coupling of Aryl Chlorides with Lithium Nucleophiles Enabled by Molecularly Defined Alkynyllithium Palladium Catalysts.

Palladium-catalyzed cross-couplings of aryl chlorides usually call for bulky, electron-rich ligands such as phosphines or heterocyclic carbenes. We have now found that similarly powerful cross-coupling catalysts are obtained by the reaction of palladium salts with alkynyllithium reagents. The species initially formed in this process was characterized as a dilithium tetraalkinyl palladate complex. It catalyzes the coupling of aryl chlorides with the lithium salts of various terminal alkynes to give alkynyl arenes. The isolated Li-alkynyl-Pd complex also efficiently promotes the reaction of aryl, and allyl chlorides with (hetero)aryl-, alkyl-, and allyllithium compounds as well as lithium amides. None of these reactions proceeded in the presence of palladium salts alone. The preparative utility of this approach was demonstrated by the synthesis of 49 molecules, including pharmaceutically relevant compounds.

Effects of a Short-Term Vegan Challenge in Older Adults on Metabolic and Inflammatory Parameters-A Randomized Controlled Crossover Study.

SCOPE: A long-term vegan diet carries the risk of insufficient protein and micronutrient intake for older adults. However, even a short-term (48 h) vegan diet exerts positive metabolic effects in younger adults. In this study, we investigate the feasibility and effects of a short-term vegan challenge on metabolic and inflammatory markers in older adults. METHOD AND RESULTS: In this randomized controlled crossover-study, 30 healthy older adults (≥65 years) are assigned to either a 48 h ad libitum vegan or omnivorous diet. During the vegan diet, participants exhibit lower protein (p = 0.001) and fat intake as well as higher carbohydrate and dietary fiber intake, resulting in a lower caloric intake (all p < 0.001). Insulin concentrations (p = 0.042) and insulin resistance (p = 0.036) decline only after the vegan diet. The study observes reductions in serum glucose (p < 0.001), triglyceride (p = 0.005), and hsCRP (p = 0.044) concentrations and weight (p < 0.001), independent of the diet. Participants with low-grade inflammation exhibit notable metabolic improvements after the vegan diet. CONCLUSION: Improvements in insulin homeostasis are observed after the vegan diet, but meeting protein requirements are not feasible during the short-term vegan challenge despite dietary counseling, which warrants concern.