Article
Chemistry, Organic
Jinfeng Huang, Yimin Jia, Xiangyu Li, Jianli Duan, Zhong-Xing Jiang, Zhigang Yang
Summary: A highly regioselective copper-catalyzed reaction has been developed for the first time to access tetrasubstituted allene derivatives containing halogen and CF3 groups with good to excellent yields. This practical and convenient method is compatible with a wide range of functional groups and has shown promising applications in the gram-scale preparation and late-stage functionalization of biologically active molecules.
Article
Chemistry, Organic
Qian Tu, Zheyuan Wang, Zhongchao Zhang, Jun Huang, Zhen Yang
Summary: The structurally intriguing tetracyclic core of complex harziane diterpenoid was successfully constructed in 14 steps from commercially available compound. Key methods used include Mn/Cu-mediated oxidative 1,3-dicarbonyl radical cascade cyclization reaction and Au-catalyzed diastereoselective formal [2 + 2] cycloaddition.
Article
Chemistry, Multidisciplinary
Wufeng Chen, Chunhui Jiang, Jianying Zhang, Jiaqi Xu, Lin Xu, Xiufang Xu, Jianfeng Li, Chunming Cui
Summary: Allenes are versatile synthons in organic synthesis and medicinal chemistry, and the efficient and selective 1,4-hydrosilylation of branched 1,3-enynes can be achieved using ene-diamido rare-earth ate catalysts, leading to the exclusive formation of tetrasubstituted silylallenes. The mechanism involves the crucial roles of high Lewis acidity, large ionic radius, and ate structure of the rare-earth catalysts, as revealed by deuteration reaction, kinetic study, and DFT calculations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Yuyang Bai, Liping Cao, Siyuan Li, Guang'an Zhang, Yingguo Liu, Fengqian Zhao, Junliang Wu
Summary: A photoredox/Lewis acid cooperative catalytic system has been developed for the construction of C-vinyl-C-Rf bonds through the dehydrative difluoroalkylation of benzyl alcohols. Various allylic gem-difluorides were obtained with moderate yields and good to excellent E/Z selectivity. Control experiments were conducted and a possible mechanism for this process was proposed.
Article
Chemistry, Organic
Lingfei Hu, Han Gao, Yanlei Hu, Xiangying Lv, Yan-Bo Wu, Gang Lu
Summary: DFT calculations and EDA were used to investigate the mechanism and origin of ligand effects on stereoinversion in Pd-catalyzed synthesis of tetrasubstituted olefins. It was found that the steric properties of the ligands lead to different stereoselectivity-determining steps, with Pauli repulsion and polarization playing dominant roles in controlling stereochemistry in 1,2- and 1,3-migrations, respectively. Differences in Pauli repulsion and polarization between the two stereoselective transition states were further identified.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Leandro Duarte de Almeida, Hongli Wang, Kathrin Junge, Xinjiang Cui, Matthias Beller
Summary: This minireview discusses the use of homogeneous noble metal catalysts and earth-abundant transition metals/heterogeneous catalysts in hydrosilylation reactions, highlighting the growing interest in more sustainable and economic catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Litao Zhou, Ruoxin Huang, Shaohang Lu, Bingxin Liu, Mingchun Gao, Bin Xu
Summary: A regio- and stereoselective direct nitration of vinylcyclopropanes with Cu(NO3)2 and KI is described, which efficiently affords nitroalkenes while preserving the cyclopropane skeleton. The method can be extended to other vinylcycles and biomolecule derivatives with a wide substrate scope, good functionality tolerance, and efficient synthesis modularity. Further transformations demonstrate the versatility of the obtained products as building blocks in organic synthesis. The proposed ionic pathway explains the intact small ring and the effect of KI during the reaction.
Article
Chemistry, Organic
Xin Gong, Na Yu, Linghui Gu, Zheyu Li, Wenbo Ma, Fei Zhao
Summary: In this study, a rhodium-catalyzed C-H alkenylation/DG migration cascade for the synthesis of tetrasubstituted 1,3-enynes from N-phenoxyacetamides and 1,3-diynes has been achieved with the assistance of the acetamido directing group (DG). Alternatively, a rhodium-catalyzed [3 + 2] annulation for the synthesis of alkynylated benzofurans from the same set of substrates has also been achieved by simply changing the reaction conditions. This work highlights the tunable divergent synthesis of valuable compounds triggered by C-H activation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Ziwei Luo, Yuwei Zong, Gavin Chit Tsui
Summary: The stereoselective C-F bond borylation of tetrasubstituted beta,beta-difluoroacrylates has been achieved using unsymmetrical diboron reagent (pin)B-B(dan) under the palladium(0)-catalyzed conditions. This method allows access to novel boronamides containing the monofluorinated vinyl-B(dan) functionality, which can directly cross-couple with gem-difluoroalkenes to afford vincinal difluoro 1,3-dienes with modular control of the substituents in Suzuki-Miyaura reactions.
Article
Chemistry, Organic
Yunhe Lv, Wanru Han, Weiya Pu, Jinhui Xie, Axue Wang, Mengyue Zhang, Jin Wang, Junrong Lai
Summary: A novel and practical copper-catalyzed reaction for 1,4-sulfonylcyanation of 1,3-enynes under mild conditions is described. The reaction provides efficient access to a variety of 5-sulfonylpenta-2,3-dienenitrile derivatives with excellent functional group tolerance and selectivity.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Biochemistry & Molecular Biology
Elizabeth S. Li, Margaret S. Saha
Summary: Novel methods for calcium ion detection have diverse applications in vitro and in vivo, especially when matched with advances in fluorescence imaging techniques. The limitations presented by organic calcium dyes, genetically encoded calcium indicators, and calcium-responsive nanoparticles suggest a potential path for more rapid optimization using a synthetic biology approach. This engineering-oriented discipline can offer a promising toolkit for interfacing with calcium signaling in eukaryotic systems.
Article
Chemistry, Organic
Yanhui Wang, Gavin Chit Tsui
Summary: A highly diastereoselective Pd(0)-catalyzed Mizoroki-Heck reaction of gem-difluoroalkenes is reported. This reaction allows for cross-coupling of a C-F and C-H bond by reacting two different alkenes through a distinct pathway. Mono-fluorinated 1,3-diene products can be synthesized with control over each alkene's geometry and good functional group tolerance.
Article
Chemistry, Multidisciplinary
Zhi-Peng Bao, Youcan Zhang, Xiao-Feng Wu
Summary: The introduction of fluorine atoms into organic molecules is an attractive topic. This work developed an interesting palladium-catalyzed reaction to transform aryl olefins into difluoropentanedioate compounds with good functional-group tolerance and high regioselectivity. Ethyl bromodifluoroacetate acts as both a difluoroalkyl precursor and a nucleophile in this reaction. Additionally, successful scale-up reactions and further transformations of the obtained product were demonstrated.
Article
Chemistry, Organic
Jinshan Li, Wenxue Xi, Saimei Liu, Chenxi Ruan, Xiaochun Zheng, Jianguo Yang, Lei Wang, Zhiming Wang
Summary: A new HFIP-catalyzed difluoroalkylation reaction has been developed for the synthesis of structurally diverse tetrasubstituted difluoroalkyl allenes from propargylic alcohols and difluoroenoxysilanes. This method allows for the rapid construction of highly functionalized multisubstituted fluorinated allenes and the synthesis of various structurally interesting fluorine-containing molecules.
Article
Chemistry, Organic
Hong-Chao Liu, Xiao-Ping Gong, Yu-Zhao Wang, Zhi-Jie Niu, Heng Yue, Xue-Yuan Liu, Yong-Min Liang
Summary: A novel Ru-catalyzed regioselective alkylarylation of vinylarenes with alkyl halides and arenes via meta-C(sp(2))-H bond functionalization has been reported. This reaction shows excellent substrate tolerance and regioselectivity, as well as redox-neutral conditions.
