Organic Photoredox-Catalyzed Hydrosilylation of Vinylboronic Esters for the Synthesis of Geminal and Vicinal Borosilanes.

Geminal and vicinal borosilanes have unique applications in functional materials and synthetic transformations. Herein, a convenient method for the synthesis of geminal and vicinal borosilanes is developed via photoredox metal-free hydrosilylation of vinylboronic esters. This strategy features the advantages of high atom economy, environmental friendliness, and excellent functional group compatibility. The mechanism studies reveal that the catalytic reaction goes through photoredox HAT catalysis and a radical addition pathway.

Photoredox Catalyzed Tandem Denitrogenative [4 + 2] Annulation of 1,2,3-Benzotriazin-4(3H)-ones with Terminal Olefins.

The dihydroisoquinolones skeleton is ubiquitous in natural products and biological molecules. Reported strategies for constructing dihydroisoquinolones usually require noble metal catalysts or stoichiometric oxidants, which limit their wide applications. Herein, we developed a photoredox catalyzed tandem denitrogenative [4 + 2] annulation reaction of 1,2,3-benzotriazin-4(3H)-ones with terminal olefins. A variety of dihydroisoquinolones can be accessed in moderate to excellent yield. This protocol features high atom-economy, mild reaction conditions, and is external oxidant-free, enabling the synthesis of various substituted dihydroisoquinolones.

Photoredox Synthesis of Silicon-Containing Isoindolin-1-ones and Deuterated Analogues Through Hydrosilylation and Deuterium-silylation.

An efficient, practical, and metal-free protocol for the synthesis of silicon-containing isoindolin-1-ones and deuterated analogues via the synergistic combination of an organic photoredox and hydrogen atom transfer process is described. This strategy features mild reaction conditions, high atom economy, and excellent functional group compatibility, delivering a myriad of structurally diverse and valuable products with good to excellent yields.

Electroreductive carboxylation of benzylphosphonium salts with CO2 through the cleavage of the C(sp3)-P bond.

Herein, a electroreductive carboxylation of benzylphosphonium salts was achieved by the cleavage of the C(sp3)-P bond, and various valuable arylacetic acids could be synthesized by this strategy. Also, based on control experiments and previous studies, a plausible reaction mechanism was proposed to explain the reaction process. The establishment of this procedure will provide a new paradigm for the functionalization of alkyl phosphonium salts.

Electrochemical benzylic deuteration of p-QMs enabling the synthesis of benzylic deuterated diarylmethanes.

Herein, electroreductive umpolung benzylic deuteration of p-QMs using cheap and easily accessible D2O as a deuterium source is reported. Various value-added benzylic deuterated diarylmethanes can be synthesized without the requirement of noble metal catalysts, redox reagents, and strong bases. The establishment of this protocol will provide an alternative strategy for acquiring benzylic deuterated diarylmethanes.

Photoredox-catalyzed C(sp2)-H trifluoromethylation of 3-methylene-isoindolin-1-ones under metal-free conditions.

A facile synthetic method for direct C(sp2)-H bond trifluoromethylation of 3-methylene-isoindolin-1-ones under visible-light-induced metal-free conditions is presented. This protocol features mild reaction conditions, broad substrate scope and excellent functional group tolerance, resulting in a range of structurally diverse trifluoromethylated products in good to excellent yields.

Magnesium-Mediated Umpolung Carboxylation of p-Quinone Methides with CO2.

Magnesium-mediated reductive carboxylation of p-QMs with CO2 via an Umpolung strategy has been developed, which can be used for the preparation of various aryl acetic acids. This protocol featured high atom economy, mild conditions, and operational simplicity. The creation of this Umpolung carboxylation of p-QMs will unprecedentedly extend the application of p-QMs to nucleophilic reagents.

Difluoromethylation-Carboxylation and -Deuteration of Alkenes Triggered by Electroreduction of Difluoromethyltriphenylphosphonium Bromide.

It is significant to develop novel difluoromethylation methods because of the important roles of difluoromethyl groups in the medicinal chemistry and material industries. Here, we developed a novel difluoromethylation-carboxylation and difluoromethylation-deuteration method triggered by a difluoromethyl radical generated by electroreduction of stable and easily available difluoromethyltriphenylphosphonium bromide. Various molecules containing difluoromethyl and carboxyl or deuterium groups can be synthesized through this method. The establishment of this method will provide an alternative to radical difluoromethylation reactions.

Photocatalytic synthesis of alkyl-alkyl sulfones via direct C(sp3)-H bond functionalization.

We report a highly efficient one-pot, three-component strategy for the construction of alkyl-alkyl sulfones through a photoinduced TBADT-catalyzed C(sp3)-H sulfonylation of unactivated hydrocarbon compounds. A wide range of commercially available hydrocarbon compounds and bioactive molecules can be successfully applied to the catalytic system, affording the corresponding alkyl-alkyl sulfones in good to excellent yields (>50 examples, up to 87% yield).

Photocatalytic Synthesis of Diarylmethyl Silanes via 1,6-Conjugate Addition of Silyl Radicals to p-Quinone Methides.

A novel photocatalytic method for the preparation of diarylmethyl silanes was reported through silyl radicals addition strategy to p-QMs (p-quinone methides). This protocol could tolerate a variety of functional groups affording the corresponding silylation products with moderate to excellent yields. The resulting silylation products could be easily converted into a series of bioactive GPR40 agonists and useful p-QMs precursors for the synthesis of compounds possessing both quaternary carbon centers and silicon substituents through simple operation. A plausible mechanism of silyl radicals to p-QMs was proposed on the basis of experimental results and previous literature.

Individual Tree Species Classification Based on Convolutional Neural Networks and Multitemporal High-Resolution Remote Sensing Images.

The classification of individual tree species (ITS) is beneficial to forest management and protection. Previous studies in ITS classification that are primarily based on airborne LiDAR and aerial photographs have achieved the highest classification accuracies. However, because of the complex and high cost of data acquisition, it is difficult to apply ITS classification in the classification of large-area forests. High-resolution, satellite remote sensing data have abundant sources and significant application potential in ITS classification. Based on Worldview-3 and Google Earth images, convolutional neural network (CNN) models were employed to improve the classification accuracy of ITS by fully utilizing the feature information contained in different seasonal images. Among the three CNN models, DenseNet yielded better performances than ResNet and GoogLeNet. It offered an OA of 75.1% for seven tree species using only the WorldView-3 image and an OA of 78.1% using the combinations of WorldView-3 and autumn Google Earth images. The results indicated that Google Earth images with suitable temporal detail could be employed as auxiliary data to improve the classification accuracy.

An Image Registration Method for Multisource High-Resolution Remote Sensing Images for Earthquake Disaster Assessment.

For earthquake disaster assessment using remote sensing (RS), multisource image registration is an important step. However, severe earthquakes will increase the deformation between the remote sensing images acquired before and after the earthquakes on different platforms. Traditional image registration methods can hardly meet the requirements of accuracy and efficiency of image registration of post-earthquake RS images used for disaster assessment. Therefore, an improved image registration method was proposed for the registration of multisource high-resolution remote sensing images. The proposed method used the combination of the Shi_Tomasi corner detection algorithm and scale-invariant feature transform (SIFT) to detect tie points from image patches obtained by an image partition strategy considering geographic information constraints. Then, the random sample consensus (RANSAC) and greedy algorithms were employed to remove outliers and redundant matched tie points. Additionally, a pre-earthquake RS image database was constructed using pre-earthquake high-resolution RS images and used as the references for image registration. The performance of the proposed method was evaluated using three image pairs covering regions affected by severe earthquakes. It was shown that the proposed method provided higher accuracy, less running time, and more tie points with a more even distribution than the classic SIFT method and the SIFT method using the same image partitioning strategy.

An Improved Pansharpening Method for Misaligned Panchromatic and Multispectral Data.

Numerous pansharpening methods were proposed in recent decades for fusing low-spatial-resolution multispectral (MS) images with high-spatial-resolution (HSR) panchromatic (PAN) bands to produce fused HSR MS images, which are widely used in various remote sensing tasks. The effect of misregistration between MS and PAN bands on quality of fused products has gained much attention in recent years. An improved method for misaligned MS and PAN imagery is proposed, through two improvements made on a previously published method named RMI (reduce misalignment impact). The performance of the proposed method was assessed by comparing with some outstanding fusion methods, such as adaptive Gram-Schmidt and generalized Laplacian pyramid. Experimental results show that the improved version can reduce spectral distortions of fused dark pixels and sharpen boundaries between different image objects, as well as obtain similar quality indexes with the original RMI method. In addition, the proposed method was evaluated with respect to its sensitivity to misalignments between MS and PAN bands. It is certified that the proposed method is more robust to misalignments between MS and PAN bands than the other methods.

Assessment of Pansharpening Methods Applied to WorldView-2 Imagery Fusion.

Since WorldView-2 (WV-2) images are widely used in various fields, there is a high demand for the use of high-quality pansharpened WV-2 images for different application purposes. With respect to the novelty of the WV-2 multispectral (MS) and panchromatic (PAN) bands, the performances of eight state-of-art pan-sharpening methods for WV-2 imagery including six datasets from three WV-2 scenes were assessed in this study using both quality indices and information indices, along with visual inspection. The normalized difference vegetation index, normalized difference water index, and morphological building index, which are widely used in applications related to land cover classification, the extraction of vegetation areas, buildings, and water bodies, were employed in this work to evaluate the performance of different pansharpening methods in terms of information presentation ability. The experimental results show that the Haze- and Ratio-based, adaptive Gram-Schmidt, Generalized Laplacian pyramids (GLP) methods using enhanced spectral distortion minimal model and enhanced context-based decision model methods are good choices for producing fused WV-2 images used for image interpretation and the extraction of urban buildings. The two GLP-based methods are better choices than the other methods, if the fused images will be used for applications related to vegetation and water-bodies.

A Novel Unsupervised Segmentation Quality Evaluation Method for Remote Sensing Images.

The segmentation of a high spatial resolution remote sensing image is a critical step in geographic object-based image analysis (GEOBIA). Evaluating the performance of segmentation without ground truth data, i.e., unsupervised evaluation, is important for the comparison of segmentation algorithms and the automatic selection of optimal parameters. This unsupervised strategy currently faces several challenges in practice, such as difficulties in designing effective indicators and limitations of the spectral values in the feature representation. This study proposes a novel unsupervised evaluation method to quantitatively measure the quality of segmentation results to overcome these problems. In this method, multiple spectral and spatial features of images are first extracted simultaneously and then integrated into a feature set to improve the quality of the feature representation of ground objects. The indicators designed for spatial stratified heterogeneity and spatial autocorrelation are included to estimate the properties of the segments in this integrated feature set. These two indicators are then combined into a global assessment metric as the final quality score. The trade-offs of the combined indicators are accounted for using a strategy based on the Mahalanobis distance, which can be exhibited geometrically. The method is tested on two segmentation algorithms and three testing images. The proposed method is compared with two existing unsupervised methods and a supervised method to confirm its capabilities. Through comparison and visual analysis, the results verified the effectiveness of the proposed method and demonstrated the reliability and improvements of this method with respect to other methods.

Bamboo Classification Using WorldView-2 Imagery of Giant Panda Habitat in a Large Shaded Area in Wolong, Sichuan Province, China.

This study explores the ability of WorldView-2 (WV-2) imagery for bamboo mapping in a mountainous region in Sichuan Province, China. A large area of this place is covered by shadows in the image, and only a few sampled points derived were useful. In order to identify bamboos based on sparse training data, the sample size was expanded according to the reflectance of multispectral bands selected using the principal component analysis (PCA). Then, class separability based on the training data was calculated using a feature space optimization method to select the features for classification. Four regular object-based classification methods were applied based on both sets of training data. The results show that the k-nearest neighbor (k-NN) method produced the greatest accuracy. A geostatistically-weighted k-NN classifier, accounting for the spatial correlation between classes, was then applied to further increase the accuracy. It achieved 82.65% and 93.10% of the producer's and user's accuracies respectively for the bamboo class. The canopy densities were estimated to explain the result. This study demonstrates that the WV-2 image can be used to identify small patches of understory bamboos given limited known samples, and the resulting bamboo distribution facilitates the assessments of the habitats of giant pandas.

Electroreductive Arylcarboxylation of Styrenes with CO2 and Aryl Halides via a Radical-Polar Crossover Mechanism.

2,3-Diaryl propanoic acids are important structures as a result of their widespread presence in numerous bioactive compounds. However, the limitations of existing synthetic techniques include the requirement for costly catalysts and limited substrates. Here, we developed a novel electroreductive arylcarboxylation of alkenes with CO2 based on a radical-polar crossover pathway assisted by easily accessible dimethyl terephthalate as a reductive mediator. This method will provide an efficient strategy for the synthesis of 2,3-diarylpropanoic acids.

Silylation and (Hetero)aryl/alkenylation of Unactivated Alkenes via Radical-Mediated Distal 1,4-Migration with Hydrosilanes under Organophotocatalysis.

We report a novel organic photoredox catalysis to achieve unprecedented γ-(hetero)aryl/alkenyl-δ-silyl aliphatic amines via silyl-mediated distal (hetero)aryl/alkenyl migration of aromatic/alkenyl amines bearing unactivated alkenes with hydrosilanes. This protocol features mild and metal-free reaction conditions, high atom economy, excellent selectivity, and functional group compatibility. Mechanistic studies suggest that silylation and (hetero)aryl/alkenylation involve photoredox hydrogen atom transfer catalysis and subsequent 1,4-migration of a remote (hetero)aryl/alkenyl group from nitrogen to carbon.

Electroreductive Cross-Coupling between Aromatic Aldehydes and Chlorosilanes Enabling the Synthesis of α-Silyl Alcohols.

α-Silyl alcohols are powerful structural motifs for pharmaceutical chemistry, materials chemistry, and organic synthesis. The limitations of current synthetic techniques encompass a requirement for difficult-to-obtain silyl precursors, noble-metal catalysts, and narrow substrate scopes. Here, we developed a general synthetic method for α-silyl alcohols through electroreductive cross-coupling of aldehydes and chlorosilane. This method features easily available reagents, mild conditions, and a wide substrate scope. The establishment of this protocol will provide an alternative for access to α-silyl alcohols.

Modular access to diarylmethyl sulfonamides via visible light-promoted cross-coupling reactions.

We report a novel and efficient method for the preparation of diarylmethyl sulfonamide derivatives through visible-light-induced sulfamoylation of para-quinone methides with sulfamoyl chlorides under mild, metal-free conditions. This protocol demonstrates excellent tolerance toward a wide range of functional groups, affording the corresponding products in moderate to high yields. Preliminary mechanism studies revealed that the excited photocatalyst rhodamine 6G* was mainly quenched by para-quinone methides and the generated diarylmethyl radical intermediates then underwent radical-radical cross-coupling with sulfamoyl radicals to yield the diarylmethyl sulfonamides.