Review
Chemistry, Applied
Shivani Sharma, Jitender Singh, Anuj Sharma
Summary: The novel concept of radical-polar crossover (RPCO) and polar-radical crossover (PRCO) reactions has emerged in recent years as a valuable tool bridging the gap between polar and radical reactions, overcoming their limitations, and improving the green quotient of reactions. The development and transformation of this area into synthetically important reactions is summarized in this review.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Fang Li, Chao Pei, Rene M. Koenigs
Summary: The study describes a photocatalytic approach for accessing triplet carbene intermediates via energy transfer to conduct efficient gem-difluoroolefination reactions, with the key role played by tertiary amines. The research explores a wide substrate scope, ranging from simple olefins to pharmaceutically relevant building blocks.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Feng Zhang, Shangteng Liao, Lu Zhou, Kai Yang, Chenglan Wang, Yixian Lou, Cece Wang, Qiuling Song
Summary: A radical-induced 1,2-alpha-boryl migration through radical polar crossover reactions has been discovered in this study. This method features high atom economy, a broad substrate scope, and good functional group toleration, with mild reaction conditions.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Hyeyun Keum, Hoimin Jung, Jiwoo Jeong, Dongwook Kim, Sukbok Chang
Summary: In this study, an intramolecular C(sp(2))-H amidation of N-acyloxyamides under photoredox conditions was reported to produce delta-benzolactams with an aryl-alkyl sigma-bond relocation. Computational studies identified the N-[3,5-bis(trifluoromethyl)benzoyl] group as the most effective amidyl radical precursor, which led to the rationalization of radical-polar crossover for ring-expansion with C-C bond migration.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Shangsheng Zhou, Yu Pu, Zhengli Liu, Xiaoming Zhang, Jiang Zhu, Zhang Feng
Summary: This study presents a novel iron-catalyzed reaction that efficiently converts unactivated gem-difluoroalkenes, gem-dichloroalkenes, and gem-dibromoalkenes into 1,2-bis(boryl)-alkanes with high selectivity and broad substrate applicability. Preliminary mechanistic studies suggest that double beta-F elimination plays a role in the catalytic cycle, with 1,1-diborylated alkenes potentially serving as intermediates in this iron-catalyzed 1,2-diborylation reaction.
Review
Chemistry, Applied
Santosh Kumar Nanda
Summary: Semipinacol rearrangement has provided elegant methods for the synthesis of complex scaffolds and is widely used in the total synthesis of natural products. Besides classical methods, the rearrangement has undergone revolutions and is now happening in an eco-friendly manner through catalytic radical-polar crossover tools. This review provides an overview of these developments.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Multidisciplinary Sciences
Kenji Ota, Kazunori Nagao, Dai Hata, Haruki Sugiyama, Yasutomo Segawa, Ryosuke Tokunoh, Tomohiro Seki, Naoya Miyamoto, Yusuke Sasaki, Hirohisa Ohmiya
Summary: This study demonstrates a light-driven radical-polar crossover mechanism for the tertiary alkylation of phosphorus atoms in nucleotides, enabling the synthesis of alkylphosphonate structures that are difficult to obtain using existing methods.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Jiabao Tian, Lei Zhou
Summary: This study describes a photocatalytic C-H gem-difunctionalization of 1,3-benzodioxoles with two different alkenes for the synthesis of highly functionalized monofluorocyclohexenes. By using 4CzIPN as the photocatalyst, the direct single electron oxidation of 1,3-benzodioxoles enables their defluorinative coupling with alpha-trifluoromethyl alkenes to produce gem-difluoroalkenes. The C-H bond of the resulting gamma,gamma-difluoroallylated 1,3-benzodioxoles can be further functionalized via radical addition to electron-deficient alkenes using a more oxidizing iridium photocatalyst, leading to the formation of monofluorocyclohexenes through carbanion capture and beta-fluoride elimination.
Article
Chemistry, Multidisciplinary
Yunxiao Zhang, Yunhong Niu, Youyuan Guo, Jiaxin Wang, Yizhi Zhang, Shanshan Liu, Xiao Shen
Summary: In this study, photocatalyzed cascade reactions between readily available cyclopropanols and alpha-trifluoromethyl-substituted olefins were reported for the synthesis of fused gem-difluorooxetanes. Two rings and three bonds were efficiently constructed in one reaction. The reaction demonstrated broad substrate scope and the downstream transformations of the products highlighted the synthetic potential. Mechanistic study supported the presence of cascade photoredox catalysis and energy transfer catalysis/direct photo-excitation processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Zhipeng Huang, Yang Yang, Junju Mu, Genheng Li, Jianyu Han, Puning Ren, Jian Zhang, Nengchao Luo, Ke-Li Han, Feng Wang
Summary: Radicals are key intermediates in reactions and their reactivity poses challenges to controlling reactions over heterogeneous catalysts. Metal nanoparticles can stabilize and manipulate free radical species generated from photo-excited TiO2, facilitating controlled radical reactions on catalyst surfaces. These insights are crucial for designing advanced heterogeneous catalytic systems.
CHINESE JOURNAL OF CATALYSIS
(2023)
Review
Chemistry, Multidisciplinary
Lei Dai, Song Ye
Summary: N-heterocyclic carbene (NHC)-catalyzed reactions involving two-electron and radical pathways have been well-established, with the former more developed than the latter in terms of reaction types and enantioselectivity. In the past decade, several elegant NHC-catalyzed radical reactions have been developed, including oxidation of aldehydes, reductive coupling reactions, and reactions via radical homoenolates.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Physical
Patrick Enders, Katrina Prane, Eric Schoenke, Tobias Taeufer, Dirk Michalik, Jabor Rabeah, Robert Francke
Summary: A photochemical rearrangement of O-aryl thiocarbamates to S-aryl compounds via heterogeneous electron transfer with photo-excited titanium dioxide is described. This rearrangement is crucial in the conversion of phenols to thiophenols. The reaction can be conducted at room temperature under aerobic conditions using violet LEDs, resulting in yields up to 99% for 24 electron-rich substrates. A plausible mechanism is proposed based on substrate scope, spectroscopic studies, and control experiments.
Review
Chemistry, Multidisciplinary
Anastasia L. Gant Kanegusuku, Jennifer L. Roizen
Summary: Photomediated Giese reactions have become a forefront in radical chemistry, utilizing organometallic photocatalysts to generate carbon-centered radicals. Chemists have developed numerous strategies to access crucial carbon-centered radical intermediates for radical conjugate addition processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Wei Sun, Yue Hu, Chungu Xia, Chao Liu
Summary: Gem-borylsilylalkanes have emerged as powerful reagents in synthetic chemistry due to their versatile transforming ability, and efforts have been made to access these motifs from easily accessible chemical feedstocks. Compared with gem-diborylalkane analogues, gem-borylsilylalkanes can be chemoselectively converted into various functionalized molecules through selective C-Si and C-B bond transformation.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Tongchang Fang, Liwei Wang, Miaomiao Wu, Xiaotian Qi, Chao Liu
Summary: The synthesis of diborodichloromethane (DBDCM) is crucial for the construction of diverse gem-diborylalkanes, and consecutive tetra-functionalizations of DBDCM allow for the construction of diverse carbon-containing molecules. Isotopically enriched C-13-DBDCM and B-10-DBDCM reagents are beneficial for the synthesis of carbon-13 and boron-10 molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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
Chemistry, Multidisciplinary
Ziqi Zhu, Lin Lin, Jieshuai Xiao, Zhuangzhi Shi
Summary: The stereo- and enantioselective cross-electrophile coupling involving C-F bond activation was successfully achieved using a chiral nickel complex and B(2)pin(2) as a stoichiometric reductant. The reaction allows the construction of a C(sp(2))-C(sp(3)) bond under mild conditions, resulting in a variety of monofluoroalkenes bearing stereogenic allylic centers. Initial mechanistic studies suggest a radical chain pathway may be involved in the C-F bond activation process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jiahang Lv, Xue-Jun Zhang, Minyan Wang, Yue Zhao, Zhuangzhi Shi
Summary: The study developed a metal-free P(III)-directed phosphine C-H borylation method, mediated by BBr3, to synthesize products containing both phosphorus and boron. The metal-free strategy features low cost, practicality, and environmental friendliness.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Mengning Wang, Xiaomei Zhang, Mengtao Ma, Binlin Zhao
Summary: Efficient palladium-catalyzed synthesis of esters from available arenes has been achieved by regioselective thianthrenation to generate aryl-TT salts, which can couple with phenol formate and N-hydroxysuccinimide formate to form phenol esters and NHS esters, respectively. A wide range of functional esters can be prepared efficiently under this redox-neutral palladium-catalytic condition. The established platform and products show potential for late-stage functionalization and synthetic applications.
Article
Chemistry, Organic
Binlin Zhao, Qiuzhu Wang, Tianxiang Zhu, Bin Feng, Mengtao Ma
Summary: In this study, a palladium-catalyzed method was developed to synthesize structurally diverse C-1 deuterated aldehydes from readily available arenes, achieving deuterium incorporation with high selectivity (96%-99%). The cost-effective DCOONa was used as a convenient deuterium source under palladium-catalytic redox neutral conditions. This catalytic approach enables direct late-stage C-H functionalization of bioactive molecules and natural product derivatives assisted by C(sp(2))-H thianthrenation, and can also be applied to prepare deuterated drugs and analogues with high levels of deuterium incorporation.
Article
Chemistry, Organic
Qiuzhu Wang, Mengning Wang, Qianhui Wu, Mengtao Ma, Binlin Zhao
Summary: This study demonstrates an efficient and operationally simple approach for the synthesis of beta-polychlorinated alkynes through a copper-catalyzed multicomponent reaction. Mechanistic experiments confirm that the copper acetylide complex plays a key role in the reaction, and the method has potential application for the synthesis of chiral beta-polychlorinated alkynes.
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
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.
Review
Chemistry, Multidisciplinary
Jiefeng Hu, Jiahang Lv, Zhuangzhi Shi
Summary: C-H bond activation and functionalization is a research hot topic in organic synthesis due to its special importance in both academic and industrial fields. C-H borylation, as a highly economic approach for generating organoborons, has attracted much attention. However, the selectivity of C(sp3)-H borylation still remains a challenge, primarily due to the ubiquity and low reactivity of alkanes.
TRENDS IN CHEMISTRY
(2022)
