ABSTRACT
The formation of one unavoidable byproduct in traditional disproportionation reactions limits their applications in synthesis. Inspired by convergent disproportionation, we develop an iodine-induced cyclization and oxidation of allylic alcohols to produce highly functionalized bicyclo[3.2.1]octanes through creation of six new bonds. Guided by the mechanism, we elaborated a variety of other bicyclo[3.2.1]octanes bearing distinct groups with presynthesized dienes and enones as the starting materials. This work provides a divergent access to bicyclo[3.2.1]octane frameworks.
ABSTRACT
Indoor occupancy detection is essential for energy efficiency control and Coronavirus Disease 2019 traceability. The number and location of people can be accurately identified and determined through classroom surveillance video analysis. This information is used to manage environmental equipment such as HVAC and lighting systems to reduce energy use. However, the mainstream one-stage YOLO algorithm still uses an anchor-based mechanism and couples detection heads to predict. This results in slow model convergence and poor detection performance for densely occluded targets. Therefore, this paper proposed a novel decoupled anchor-free VariFocal loss convolutional network algorithm DFV-YOLOv5 for occupancy detection to tackle these problems. The proposed method uses the YOLOv5 algorithm as a baseline. It uses the anchor-free mechanism to reduce the number of design parameters needing heuristic tuning. Afterwards, to reduce the coupling of the model, speed up the model's convergence ability, and improve the model detection performance, the detection head is decoupled based on the YOLOv5 model. It can resolve the conflict between classification and regression tasks. In addition, we use the VariFocal loss to assign more weights to difficult data points to optimize the class imbalance problem and use the training target q to measure positive samples, treating positive and negative samples asymmetrically. The total loss function is redesigned, the L 1 loss is increased, and the ablation experiment verifies the effect of the improved loss. By applying a hybrid activation function of the sigmoid linear unit and rectified linear unit, we improved the model's nonlinear representation and reduced the model's inference time. Finally, a classroom dataset was constructed to validate the occupancy detection performance of the model. The proposed model was compared with mainstream target detection models regarding average mean precision, memory allocation, execution time, and the number of parameters on the VOC2012, CrowdHuman and self-built datasets. The experimental results show that the method significantly improves the detection accuracy and robustness, shortens the inference time, and proves the practicality of the algorithm in occupancy detection compared with the mainstream target detection model and related variants of the model.
ABSTRACT
By complementing traditional transition metal catalysis, photoinduced catalysis has emerged as a versatile and sustainable way to achieve carbon-heteroatom bond formation. This work discloses a visible-light-induced reaction for the formation of a C-S bond from aryl halides and inorganic sulfuration agents via electron donor-acceptor (EDA) complex photocatalysis. Divergent formations of organic sulfide and disulfide have been demonstrated under mild conditions. Preliminary mechanistic studies suggest that visible-light-induced intracomplex charge transfer within the monosulfide-anion-containing EDA complex permits the C-S bond construction reactivity.
ABSTRACT
Reported herein is the first metal-free oxidative [4 + 2] coupling of o-phenylenediamines with various alkenes. Differing from the known strategy that hinged on reactive π-allyl Pd intermediates from restrained allylic alcohol/acetate and diene substrates, this metal-free method features easy accessibility of starting materials, step economy, benign reaction conditions, and more importantly broad C-C double bonds (styrenes, vinyl (thio)ethers, benzofurans, indoles) with diastereospecificities. Mechanistic studies suggest the intermediacy of the benzoquinone diimides, a class of useful but yet underexploited synthons. Of note, they efficiently furnished functionalized tetrahydroquinoxalines and complement the well-studied alkene vicinal diamination typically toward acyclic diamine derivatives.
