In this paper, we report the synthesis of alkyl-tethered alkynes through ozone-mediated and FeII-catalyzed dealkenylative alkynylation of unactivated alkenes in the presence of alkynyl sulfones. This one-pot reaction, which employs a combination of a catalytic FeII salt and l-ascorbic acid, proceeds under mild conditions with good efficiency, high stereoselectivity, and broad functional group compatibility. In contrast to our previous FeII-mediated reductive fragmentation of α-methoxyhydroperoxides, the FeII-catalyzed process was devised through a thorough kinetic analysis of the multiple competing radical (redox) pathways. We highlight the potential of this dealkenylative alkynylation through multiple post-synthetic transformations and late-stage diversifications of complex molecules, including natural products and pharmaceuticals.

Monitoring data transfer performance is a crucial task in scientific computing networks. By predicting performance early in the communication phase, potentially sluggish transfers can be identified and selectively monitored, optimizing network usage and overall performance. A key bottleneck to improving the predictive power of machine learning (ML) models in this context is the issue of class imbalance. This project focuses on addressing the class imbalance problem to enhance the accuracy of performance predictions. In this study, we analyze and compare various augmentation strategies, including traditional oversampling methods and generative techniques. Additionally, we adjust the class imbalance ratios in training datasets to evaluate their impact on model performance. While augmentation may improve performance, as the imbalance ratio increases, the performance does not significantly improve. We conclude that even the most advanced technique, such as CTGAN, does not significantly improve over simple stratified sampling.

This paper describes a catalytic asymmetric Staudinger-aza-Wittig reaction of (o-azidoaryl)malonates, allowing access to chiral quaternary oxindoles through phosphine oxide catalysis. We designed a novel HypPhos oxide catalyst to enable the desymmetrizing Staudinger-aza-Wittig reaction through the PIII/PV═O redox cycle in the presence of a silane reductant and an IrI-based Lewis acid. The reaction occurs under mild conditions, with good functional group tolerance, a wide substrate scope, and excellent enantioselectivity. Density functional theory revealed that the enantioselectivity in the desymmetrizing reaction arose from the cooperative effects of the IrI species and the HypPhos catalyst. The utility of this methodology is demonstrated by the (formal) syntheses of seven alkaloid targets: (-)-gliocladin C, (-)-coerulescine, (-)-horsfiline, (+)-deoxyeseroline, (+)-esermethole, (+)-physostigmine, and (+)-physovenine.