Article
Chemistry, Multidisciplinary
Jake W. Wilson, Bo Su, Makoto Yoritate, Jake X. Shi, John F. Hartwig
Summary: We report the iridium-catalyzed, stereoselective conversion of secondary alcohols or ketones to anti-1,3-diols by the silylation of secondary C-H bonds ? to oxygen and oxidation of the resulting oxasilolane. The silylation occurs with high selectivity at a secondary C-H bond ? to oxygen over distal primary or proximal secondary C-H bonds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jake W. Wilson, Bo Su, Makoto Yoritate, Jake X. Shi, John F. Hartwig
Summary: In this paper, we report the iridium-catalyzed conversion of secondary alcohols or ketones to anti-1,3-diols. This conversion is achieved through the silylation of secondary C-H bonds and subsequent oxidation of the resulting oxasilolane. The silylation occurs selectively at secondary C-H bonds ? to oxygen, and the catalyst used in this process is formed from a simple bisamidine ligand, which provides a long catalyst lifetime.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Isaac Choi, Antonis M. Messinis, Xiaoyan Hou, Lutz Ackermann
Summary: The research reveals osmaelectrocatalyzed C-H activations using benzoic acids, enabling electrooxidative alkyne annulations with high levels of selectivity. Unprecedented osmium(0) and osmium(II) intermediates were isolated, and detailed mechanistic studies unveiled a facile C-H cleavage and ample substrate scope for annulated heterocycles synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jyoti Dhankhar, Micha D. Hofer, Anthony Linden, Ilija Coric
Summary: This article presents a new selectivity mode for C-H arylation reactions, which is the preference for C(sp(2))-H activation next to alkyl groups. The study results indicate that this preference is related to the non-covalent interactions between the catalyst and the substrate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Anton Kudashev, Olivier Baudoin
Summary: A ligand-controlled site-selective C(sp(3))-H arylation of heteroaromatic ketones has been developed using Pd catalysis, with selective reactions occurring at the alpha- or beta-position of the ketone side-chain. Addition of a pyridone ligand enables switching from alpha- to beta-arylation. The alpha-arylation process demonstrates broad scope and high site- and chemoselectivity, while the beta-arylation is more limited, with mechanistic investigations suggesting different pathways for the two processes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Multidisciplinary
Bin Li, Pierre H. Dixneuf
Summary: Metal-catalyzed silylation reactions play a crucial role in the synthesis of organometallic compounds, especially in the activation of sp(3)C-H bonds. By utilizing different metal catalysts, intermolecular and intramolecular sp(3)C-H bond silylations directed by nitrogen-containing heterocycles or amide functions can be achieved for the formation of stable organometallic species.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Xue-Ya Gou, Yuke Li, Wei-Yu Shi, Yu-Yong Luan, Ya-Nan Ding, Yang An, Yan-Chong Huang, Bo-Sheng Zhang, Xue-Yuan Liu, Yong-Min Liang
Summary: This paper describes a new ruthenium-catalyzed method for the ortho- and meta-C-Ar-H glycosylation, resulting in the synthesis of various C-aryl pyranosides and furanosides. The method shows broad substrate scope and compatibility with different N-heterocyclic directing groups. Mechanistic studies suggest different pathways for ortho- and meta-C-Ar-H glycosylation, and density functional theory calculations provide an explanation for the high stereoselectivity observed in the meta-C-Ar-H glycosylation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Qiyuan He, Naoto Chatani
Summary: The palladium-catalyzed [3+2] annulation of aromatic amides with maleimides via the activation of ortho benzylic C-H and meta C-H bonds is reported, with a key role played by the presence of a 2-methylthiophenyl directing group for the success of the reaction. The irreversible cleavage of these C-H bonds leads to the formation of five-membered cyclic products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Bo Su, John F. Hartwig
Summary: This review discusses the rapid development and significance of enantioselective silylation and borylation of C-H bonds, emphasizing the importance of designing and developing chiral ligands for these reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Raghunath Bag, Nagendra K. Sharma
Summary: This study presents a convenient synthetic method for the Pd-catalyzed picolinamide-directed site-selective C(sp(2))-H chalcogenation of alpha-amino acids and peptides. It has been successfully applied to the synthesis of a variety of alpha-amino acids, benzylamines, and phenethyl amines with moderate to good yields and good selectivity. Moreover, it allows for late-stage peptide chalcogenation and offers wide substrate scopes and various postsynthetic utilities.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Ganesh Pandey, Sandip Kumar Tiwari, Pushpendra Singh, Pradip Kumar Mondal
Summary: The photocatalytic regiospecific p-silylation of arenes has been achieved through the coupling of in situ generated silyl radical with arene radical cation. The p-silylated arenes can be further utilized for exclusive o-silylation reaction, regiospecific o-acylation, and o-alkylation reaction.
Article
Chemistry, Applied
Keita Anoyama, Gen Onodera, Tsutomu Fukuda, Masanari Kimura
Summary: An iridium-catalyzed ortho-C-H silylation of 2-arylpyridine derivative with hydrosilane by using phosphine-borane ligand has been developed. This reaction yields mono- and disilylated products in 81-99% yields, using various 2-arylpyridines. The length of the linkage between phosphorus and boron is crucial for the reaction to proceed.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Lanxiao Zhao, Xianghui Shi, Jianhua Cheng
Summary: This study demonstrated the catalytic regioselective C-H silylation of alkoxy-substituted benzene derivatives using a specific calcium complex, offering an efficient and direct method for synthesizing silyl-substituted aromatic ether derivatives while avoiding transition metal. Proposed calcium anisyl complexes were isolated and structurally characterized as catalytic reaction intermediates.
Article
Chemistry, Multidisciplinary
Shuai Chen, Xueying Guo, Haoran Hou, Shasha Geng, Zhengli Liu, Yun He, Xiao-Song Xue, Zhang Feng
Summary: The development of aryl alkyl sulfides as dichotomous electrophiles for site-selective silylation via C-S bond cleavage has been achieved. Iron-catalyzed selective cleavage of C(aryl)-S bonds can occur in the presence of beta-diketimine ligands, and the cleavage of C(alkyl)-S bonds can be achieved by t-BuONa without the use of transition metals, resulting in the corresponding silylated products in moderate to excellent yields. Mechanistic studies suggest that Fe-Si species may undergo metathesis reactions during the cleavage of C(aryl)-S bonds, while silyl radicals are involved during the cleavage of C(alkyl)-S bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Shrikant M. Khake, Ken Yamazaki, Yusuke Ano, Naoto Chatani
Summary: This study reports a branch-selective C-H alkenylation method using an iridium catalyst with alkenes, suitable for aniline derivatives containing a pyrimidine-directing group, offering a broad substrate scope and tolerating various functional groups. The origin of branch selectivity was investigated using density functional theory calculations.
Article
Chemistry, Organic
Huanhuan Luo, Dawei Wang, Minyan Wang, Zhuangzhi Shi
Summary: Organophosphines are important ligands widely used in organic chemistry. Although progress has been made in the construction of new phosphines through Rh- or Ru-catalyzed C-H bond functionalizations, diverse phosphines remain a challenge. The described efficient process allows for the generation of various alkenylated and 2',6'-dialkenylated biarylphosphines with high selectivity.
Article
Engineering, Environmental
Zhi-Feng Chen, Qin-Bao Lin, Ben Dong, Huai-Ning Zhong, Zhi-Wei Wang
Summary: This study used UVVis and UPLC-Q-TOFMS techniques combined with chemometrics to provide spectral and mass fingerprinting for PE, developing two methods to distinguish recycled and virgin PE. The UV-Vis combined with chemometrics proved to be a more accessible, simpler, and faster approach for discrimination. The UV spectrum region of 237-331 nm was identified as a marker region, while UPLC-Q-TOF-MS detected 2314 ions and identified 48 candidate chemicals, highlighting the importance of strict identification and classification when using recycled PE as food contact material.
JOURNAL OF HAZARDOUS MATERIALS
(2022)
Article
Multidisciplinary Sciences
Dingyi Wang, Mingjie Li, Chengdong Shuang, Yong Liang, Yue Zhao, Minyan Wang, Zhuangzhi Shi
Summary: The authors report a method that appends arenes to arylphosphines via rhodium-catalyzed P(III)-directed ortho C-H activation, enabling one-fold, two-fold, and three-fold direct arylation of these compounds. This method provides a solution to the challenges associated with the modular preparation of biaryl monophosphines.
NATURE COMMUNICATIONS
(2022)
Article
Engineering, Environmental
Hanke Li, Xuefeng Wu, Siliang Wu, Lichang Chen, Xiaoxue Kou, Ying Zeng, Dan Li, Qinbao Lin, Huaining Zhong, Tianying Hao, Ben Dong, Sheng Chen, Jianguo Zheng
Summary: Machine learning algorithms were used to distinguish between virgin PET and recycled PET samples with high accuracy, demonstrating their reliability and potential for boosting the application of rPET bottles in food packaging.
JOURNAL OF HAZARDOUS MATERIALS
(2022)
Article
Engineering, Environmental
Siliang Wu, Xuefeng Wu, Hanke Li, Dan Li, Jianguo Zheng, Qinbao Lin, Cristina Nerin, Huaining Zhong, Ben Dong
Summary: A non-targeted method for screening the semi-volatile compounds of mechanically recycled PET for food contact materials was developed, and multiple chemometrics methods were used to analyze the data and investigate the potential influence factors. The results showed that total dissolution with comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry was the most effective method. 97 compounds were classified into 4 levels based on their difference levels, with 1-Methyl-2-pyrrolidinone recognized as the primary difference indicator. The contaminant was mainly derived from residuum of non-food consumer products. The specific types of contaminants and process parameters of the recycling, such as moisture content, properties of rPET, and temperature, were found to be potential key factors affecting the presence of semi-volatile compounds in mechanically recycled rPET.
JOURNAL OF HAZARDOUS MATERIALS
(2022)
Article
Chemistry, Organic
Yan Zhang, Wen Liu, Yuenian Xu, Yong Liu, Jiajian Peng, Minyan Wang, Ying Bai, Hua Lu, Zhuangzhi Shi, Xinxin Shao
Summary: A family of electrophilic deuterated methylthiolating reagents has been developed, which can be synthesized from inexpensive d4-MeOH in a few steps with high yields. These reagents serve as powerful tools for deuterated methylthiolation reactions with various nucleophiles or electrophiles under mild conditions. The structure-reactivity research conducted in this study opens up a new avenue for the development of deuterated methylthiolating reagents and efficient methodologies for trideuteromethylthiolation.
Article
Chemistry, Multidisciplinary
Lin Lin, Xue-jun Zhang, Xinyu Xu, Yue Zhao, Zhuangzhi Shi
Summary: This study reports a modular assembly method for diverse phosphine-amide ligands, using ruthenium-catalyzed C-H activation of phosphines with isocyanate directed by phosphorus(III) atoms. The method enables efficient and selective synthesis of various phosphine-amide ligands, some of which show excellent efficiency for asymmetric catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Ronghui Huang, Minyan Wang, Hong Deng, Jingkai Xu, Hong Yan, Yue Zhao, Zhuangzhi Shi
Summary: In this study, an effective method for the synthesis of phosphacycles through nickel-catalyzed heteroannulation of internal alkynes with aminophosphanes derived from o-haloanilines was reported. The method exhibits a broad scope and allows the preparation of 2-λ5-phosphaquinolines with different steric and electronic properties for fine-tuning photophysical properties. Mechanistic studies provide insights into the heteroannulation pathway and reasons for stereospecificity.
Article
Chemistry, Multidisciplinary
Jieshuai Xiao, Minyan Wang, Xuwen Yin, Shuo Yang, Pei Gu, Xueli Lv, Yue Zhao, Zhuangzhi Shi
Summary: The first asymmetric reductive (hetero)arylations of imines using aryl and heteroaryl halides enabled by a chiral cobalt-bisphosphine catalyst are reported. This approach shows good functional group compatibility and complements the reported strategy without use of organometallic reagents. Mechanistic investigations supported that aryl-cobalt, instead of an arylzinc reagent, was formed in situ in this reductive aryl-addition event.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Engineering, Environmental
Ben Dong, Xuefeng Wu, Siliang Wu, Hanke Li, Qi-Zhi Su, Dan Li, Qinbao Lin, Sheng Chen, Jianguo Zheng, Lei Zhu, Huai-Ning Zhong
Summary: A comparison was made on different methods for detecting volatile contaminants in recycled PET flakes, and HS-SPME-GCxGC-QTOF-MS was found to be a sensitive and accurate method for analyzing rPET flakes collected from recycling plants in China. 212 VCs were tentatively identified, with potential sources including plastic, food, and cosmetics. The study revealed significant differences in VCs among different recycling regions, and the chemometrics analysis selected volatile markers that differed significantly between these regions.
JOURNAL OF HAZARDOUS MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Wang Jiang, Xiuxiu Yang, Lin Lin, Chaoguo Yan, Yue Zhao, Minyan Wang, Zhuangzhi Shi
Summary: Metal-catalyzed C-H activation strategies provide an efficient approach for synthesis. In this study, visible-light-induced late-stage C-H activation was achieved using a single rhodium complex. The reaction offers advantages such as environmental friendliness and the utilization of inherent directing groups, providing a new platform for ligand design and preparation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Tianhang Wang, Zheng-Jun Wang, Minyan Wang, Lei Wu, Xiaowu Fang, Yong Liang, Jiahang Lv, Zhuangzhi Shi
Summary: This study presents a general strategy for constructing beta-borylenamides through C-H borylation, which provides a versatile means of creating stereodefined enamides. The unique advantage of this methodology lies in its stereoconvergent nature, allowing for the utilization of starting materials with both E and Z configurations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Longlong Xi, Minyan Wang, Yong Liang, Yue Zhao, Zhuangzhi Shi
Summary: The authors describe a catalytic system that can selectively alkynylate different positions on azaarenes through rhodium catalysis. This method enables precise activation of C-H bonds and offers transformative methods for accessing complex molecular architectures.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Chong Lian, Longlong Xi, Yu Yuan, Zhuangzhi Shi, Minyan Wang
Summary: An effective method for the construction of difluoromethylated alkenes through Cu-catalysed controllable hydrodefluorination of trifluoromethylated alkenes is described. This method provides an alternative approach towards diverse difluoromethyl-containing alkenes in good to excellent yields with an E-configuration. The hydrodefluorination process involves defluorinative borylation to generate gem-difluoroallylic boronates and subsequent hydrodeborylation.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Man Tang, Wenyan Zhu, Huaxing Sun, Jing Wang, Su Jing, Minyan Wang, Zhuangzhi Shi, Jiefeng Hu
Summary: Efficient synthesis methods for organosilanes are important in the fields of synthetic chemistry and materials science. In this study, an alkoxide base-promoted deborylative silylation reaction was developed, providing straightforward access to valuable organosilanes. This method demonstrates operational simplicity, broad substrate scope, excellent functional group compatibility, and convenient scalability, making it an effective and complementary platform for generating diversified benzyl silanes and silylboronates. Detailed experimental results and mechanistic studies revealed unique features of the C-Si bond formation.
