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result(s) for
"Wang, Shengchun"
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Visible light-induced direct α C–H functionalization of alcohols
2019
Considering the synthetic value of introducing active alcoholic hydroxyl group, developing C–H functionalization of alcohols is of significance. Herein, we present a photochemical method that under visible light irradiation, selectfluor can effectively promote the oxidative cross-coupling between alcohols and heteroarenes without the external photocatalysis, achieving the selective α sp
3
C–H arylation of alcohol, even in the presence of ether. The N-F activation of selectfluor under blue LEDs irradiation is evidenced by electron paramagnetic resonance (EPR) study, which is the key process for the oxidative activation of α sp
3
C–H alcohols. The observed reactivity may have significant implications for chemical transformations.
Alcohols are very useful building blocks in organic synthesis, however C–H functionaliztion in presence of free –OH groups is highly challenging. Here, the authors report a selective visible light-promoted α-functionalization of free alcohols with heteroarenes mediated by Selectofluor.
Journal Article
Electrooxidative para-selective C–H/N–H cross-coupling with hydrogen evolution to synthesize triarylamine derivatives
2019
Oxidative C–H/N–H cross-coupling is one of the most atom-economical methods for the construction of C–N bonds. However, traditional oxidative C–H/N–H cross-coupling either required the use of strong oxidants or high reaction temperature, which makes it difficult to tolerate redox active functional groups. Herein we describe an external chemical oxidant-free electrooxidative C–H/N–H cross-coupling between electron-rich arenes and diarylamine derivatives. Under undivided electrolytic conditions, a series of triarylamine derivatives are produced from electron-rich arenes and diarylamine derivatives with high functional group tolerance. Both of the coupling partners are redox active in oxidative C–H/N–H cross-coupling, which enables high regioselectivity in C–N bond formation. Exclusive
para
-selectivity is observed for the coupling with anilines.
Oxidative C–H/N–H cross-coupling is a convenient method to construct C–N bonds, however this is rarely achieved in a sustainable manner. Here, the authors show an oxidant-free electrochemical C–H/N–H cross-coupling between electron-rich arenes and diarylamines to afford triarylamines with exclusive
para
-selectivity.
Journal Article
Electrooxidation enables highly regioselective dearomative annulation of indole and benzofuran derivatives
2020
The dearomatization of arenes represents a powerful synthetic methodology to provide three-dimensional chemicals of high added value. Here we report a general and practical protocol for regioselective dearomative annulation of indole and benzofuran derivatives in an electrochemical way. Under undivided electrolytic conditions, a series of highly functionalized five to eight-membered heterocycle-2,3-fused indolines and dihydrobenzofurans, which are typically unattainable under thermal conditions, can be successfully accessed in high yield with excellent regio- and stereo-selectivity. This transformation can also tolerate a wide range of functional groups and achieve good efficiency in large-scale synthesis under oxidant-free conditions. In addition, cyclic voltammetry, electron paramagnetic resonance (EPR) and kinetic studies indicate that the dehydrogenative dearomatization annulations arise from the anodic oxidation of indole into indole radical cation, and this process is the rate-determining step.
Enriching the chemical space of polycyclic heterocycles is of high value in chemical biology. Here, the authors report an electrooxidative protocol for the regioselective dearomative annulation of indoles and benzofurans under undivided cell conditions and obtain five- to eight-membered fused heterocycles.
Journal Article
Organozinc pivalates for cobalt-catalyzed difluoroalkylarylation of alkenes
2021
Installation of fluorine into pharmaceutically relevant molecules plays a vital role in their properties of biology or medicinal chemistry. Direct difunctionalization of alkenes and 1,3-dienes to achieve fluorinated compounds through transition-metal catalysis is challenging, due to the facile β-H elimination from the Csp
3
‒[M] intermediate. Here we report a cobalt-catalyzed regioselective difluoroalkylarylation of both activated and unactivated alkenes with solid arylzinc pivalates and difluoroalkyl bromides through a cascade Csp
3
‒Csp
3
/Csp
3
‒Csp
2
bond formation under mild reaction conditions. Indeed, a wide range of functional groups on difluoroalkyl bromides, olefins, 1,3-dienes as well as (hetero)arylzinc pivalates are well tolerated by the cobalt-catalyst, thus furnishing three-component coupling products in good yields and with high regio- and diastereoselectivity. Kinetic experiments comparing arylzinc pivalates and conventional arylzinc halides highlight the unique reactivity of these organozinc pivalates. Mechanistic studies strongly support that the reaction involves direct halogen atom abstraction via single electron transfer to difluoroalkyl bromides from the in situ formed cobalt(I) species, thus realizing a Co(I)/Co(II)/Co(III) catalytic cycle.
Transition metal-catalyzed regioselective difunctionalizations of alkenes with two different functional groups are useful for preparing organic compounds, but the construction of two new C–C bonds is challenging. Here, the authors report cobalt-catalyzed regioselective difluoroalkylarylation of alkenes with solid arylzinc pivalates and difluoroalkyl bromides, through a cascade Csp
3
‒Csp
3
/Csp
3
‒Csp
2
bond formation.
Journal Article
Direct electrochemical oxidation of alcohols with hydrogen evolution in continuous-flow reactor
2019
Alcohol oxidation reactions are widely used for the preparation of aldehydes and ketones. The electrolysis of alcohols to carbonyl compounds have been underutilized owing to low efficiency. Herein, we report an electrochemical oxidation of various alcohols in a continuous-flow reactor without external oxidants, base or mediators. The robust electrochemical oxidation is performed for a variety of alcohols with good functional group tolerance, high efficiency and atom economy, whereas mechanistic studies support the benzylic radical intermediate formation and hydrogen evolution. The electrochemical oxidation proves viable on diols with excellent levels of selectivity for the benzylic position.
Alcohol oxidation to carbonyl compounds is a very useful functional group transformation in organic synthesis. Here, the authors perform the direct electrochemical oxidation of various alcohols to the corresponding ketones in a continuous-flow reactor without external oxidants, base or mediators.
Journal Article
Photo-induced oxidant-free oxidative C–H/N–H cross-coupling between arenes and azoles
by
Liu, Jiamei
,
Wang, Shengchun
,
Liu, Tianyi
in
639/638/403/933
,
639/638/439/890
,
639/638/77/888
2017
Direct cross-coupling between simple arenes and heterocyclic amines under mild conditions is undoubtedly important for C–N bonds construction. Selective C(sp
2
)-H amination is more valuable. Herein we show a selective C(sp
2
)-H amination of arenes (alkyl-substituted benzenes, biphenyl and anisole derivatives) accompanied by hydrogen evolution by using heterocyclic azoles as nitrogen sources. The reaction is selective for C(sp
2
)-H bonds, providing a mild route to
N
-arylazoles. The KIE (kinetic isotope effect) experiment reveals the cleavage of C–H bond is not involved in the rate-determining step. Kinetic studies indicate the first-order behaviour with respect to the arene component. It is interesting that this system works without the need for any sacrificial oxidant and is highly selective for C(sp
2
)-H activation, whereas C(sp
3
)-H bonds are unaffected. This study may have significant implications for the functionalization of methylarenes which are sensitive to oxidative conditions.
Functionalization of unactivated C–H bonds is an attractive strategy to introduce functionality without the need for pre-functionalized starting materials. Here the authors combine cobalt catalysis with photoredox catalysis, allowing arene-azole cross-coupling under oxidant-free conditions.
Journal Article
1,2-Amino oxygenation of alkenes with hydrogen evolution reaction
2022
1,2-Amino oxygenation of alkenes has emerged as one of the most straightforward synthetic methods to produce β-amino alcohols, which are important organic building blocks. Thus, a practical synthetic strategy for 1,2-amino oxygenation is highly desirable. Here, we reported an electro-oxidative intermolecular 1,2-amino oxygenation of alkenes with hydrogen evolution, removing the requirement of extra-oxidant. Using commercial oxygen and nitrogen sources as starting materials, this method provides a cheap, scalable, and efficient route to a set of valuable β-amino alcohol derivatives. Moreover, the merit of this protocol has been exhibited by its broad substrate scope and good application in continuous-flow reactors. Furthermore, this method can be extended to other amino-functionalization of alkenes, thereby showing the potential to inspire advances in applications of electro-induced
N
-centered radicals (NCRs).
1,2-Aminoxygenation of alkenes without extra oxidant is a practical yet challenging way to prepare β-amino alcohols. Here, the authors report an electro-oxidative route achieving such a goal with H2 evolution, exhibiting broad scope and application potential.
Journal Article
A Rail Profile Measurement Method Based on Polarization Fusion Imaging
2025
The smooth area on the rail surface causes abnormal exposure in the laser section image, resulting in measurement errors of the rail profile. To address this issue, a novel rail profile measurement technique based on polarization fusion imaging is proposed. A polarized camera is utilized to acquire the four-directional polarization component images, Stokes parameter images, linear polarization angle images, and linear polarization degree images of the rail laser section. A polarization image data fusion algorithm based on Segmented Random Sample Consensus (S-RANSAC) is designed using these images as data sources, and the optimal rail profile fitting curve is obtained. Experimental results demonstrate that the proposed method can still obtain accurate and effective rail profile data in regions where traditional methods fail to capture profile data. Compared with the traditional method, the measurement error of the rail profile is reduced from 0.137 mm to 0.081 mm, and the measurement accuracy is improved by 40.9%. Evidently, this method avoids data loss in key areas of the rail profile caused by local underexposure, thus significantly enhancing the measurement accuracy. This method can provide a valuable reference for high-precision measurement of the rail profile under complex working conditions.
Journal Article
Text Summarization Method Based on Gated Attention Graph Neural Network
by
Huang, Jingui
,
Wu, Wenya
,
Wang, Shengchun
in
Artificial intelligence
,
attention mechanism
,
Computational linguistics
2023
Text summarization is an information compression technology to extract important information from long text, which has become a challenging research direction in the field of natural language processing. At present, the text summary model based on deep learning has shown good results, but how to more effectively model the relationship between words, more accurately extract feature information and eliminate redundant information is still a problem of concern. This paper proposes a graph neural network model GA-GNN based on gated attention, which effectively improves the accuracy and readability of text summarization. First, the words are encoded using a concatenated sentence encoder to generate a deeper vector containing local and global semantic information. Secondly, the ability to extract key information features is improved by using gated attention units to eliminate local irrelevant information. Finally, the loss function is optimized from the three aspects of contrastive learning, confidence calculation of important sentences, and graph feature extraction to improve the robustness of the model. Experimental validation was conducted on a CNN/Daily Mail dataset and MR dataset, and the results showed that the model in this paper outperformed existing methods.
Journal Article
The association between occupational silica exposure and leukemia: a systematic review and meta-analysis of cohort studies
2025
Respirable crystalline silica is a proven lung carcinogen, but there is limited information of the carcinogenic effects of silica on non-respiratory organs. We aimed to systematically review cohort studies and conduct a meta-analysis to explore the relationship between occupational exposure to silica and the risk of leukemia development. We performed an exhaustive search across three databases (PubMed, Embase, and Web of Science) to identify pertinent cohort studies published since 1987. After removing duplicates and excluding irrelevant studies, 22 studies were included in our analysis. We utilized fixed-effects models in the implementation of our meta-analysis. The combined relative risk of leukemia associated with occupational silica exposure was determined to be 1.11 (95% CI: 0.93–1.33), with no significant differences observed across various industries, geographic regions, exposure periods, or study quality estimates. The present study based on cohort studies provide no evidence that occupational exposure to silica does increase the risk of leukemia.
Journal Article