Article
Chemistry, Multidisciplinary
Wei Sun, Meng-Yang Hu, Zhan-Sheng Lu, Ming-Yao Huang, Xin-Yu Zhang, Shou-Fei Zhu
Summary: This article reports a method for stereoselective transformation using an iron catalyst to synthesize Z-allylsilanes with high regioselectivity and exclusive stereoselectivity from E/Z mixtures. The mechanism of this reaction differs from previously reported mechanisms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Fen You, Jingjing Zhai, Yat-Ming So, Xiaochao Shi
Summary: A series of rare-earth metal alkyl complexes were successfully synthesized in this study, which could efficiently catalyze the living polymerization of isoprene and beta-myrcene with high cis-1,4-selectivity. Moreover, the complexes could also promote the polymerization of butadiene and its copolymerization with isoprene to produce copolymers with high cis-1,4-selectivity and narrow polydispersity.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Mahesh M. Parsutkar, T. V. RajanBabu
Summary: This study presents a new cobalt(I)-catalyzed regio- and enantioselective hydroacylation reaction of dienes, providing chiral products containing ketone functionality. Different classes of dienes show distinct regioselectivity during the reaction, and a mechanism involving a Co(I)/Co(III) oxidative dimerization cycle is proposed. The efficient syntheses of commercial relevant compounds using this method demonstrate its practical utility.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Zhi-Lin Liu, Zhi-Peng Ye, Yi-Xuan Chen, Yu Zheng, Zhen-Zhen Xie, Jian-Ping Guan, Jun-An Xiao, Kai Chen, Hao-Yue Xiang, Hua Yang
Summary: We describe a highly modular 1,4-difunctionalization of 1,3-dienes with bromodifluoroacetamides and sulfinates/amines through a photoinduced palladium-catalyzed radical relay process. This protocol offers a facile and general route to access a variety of value-added CF2-incorporated alkenes in moderate to good yields. The versatility and flexibility of this approach have been well demonstrated by readily accessible starting materials, synthetic convenience, and wide functional group compatibility.
Article
Chemistry, Organic
Ming-Hang Bi, Ying Cheng, Wen-Jing Xiao, Jia-Rong Chen
Summary: This study describes a selective three-component 1,4-difluoroalkylesterification enabled by dual photoredox and copper catalysis. The protocol utilizes commercially available CF2-reagents as radical precursors and carboxylic acids as oxygen-based nucleophiles, allowing access to difluoroalkylated allylic esters. Furthermore, this protocol can also be extended to intramolecular two-component 1,4-difluoroalkylesterification for the synthesis of 3-substituted benzobutyrolactones. Preliminary mechanistic studies provide evidence for a radical process.
Article
Chemistry, Organic
Yusuke Tomita, Naoto Haraguchi, Sayori Kiyota, Nobuyuki Komine, Masafumi Hirano
Summary: A traditional cobalt catalyst system has been found to exhibit previously undiscovered reactivity. Depending on the choice of tertiary phosphines and substrates, this catalytic system can catalyze diverse cycloadditions, yielding various cyclic compounds. The bite angles of the ligands used significantly contribute to the catalytic diversity.
Article
Chemistry, Organic
Chang-Sheng Kuai, Bing-Hong Teng, Da-Lie An, Yingying Zhao, Xiao-Feng Wu
Summary: A palladium-catalyzed carbonylation of 2-trifluoromethyl-1,3-enynes has been developed, providing access to multisubstituted conjugated dienes. This method exhibits excellent regio- and exclusive (E)-stereoselectivity and demonstrates broad substrate scope with both amines and alcohols as reaction partners, showing promising functional group tolerance.
Article
Chemistry, Physical
Ruoshui Xu, Laurence N. Rohde, Steven T. Diver
Summary: A regioselective Cu-catalyzed formal hydroboration of 1,3-disubstituted-1,3-dienes is reported. Highly substituted 1,3-dienes produced through catalytic ene-yne metathesis serve as substrates for the regioselective hydroboration with variable substituents. The reaction can be achieved with both achiral and enantioselective conditions.
Article
Chemistry, Multidisciplinary
Ke Chen, Hongdan Zhu, Shuang Liu, Jiahui Bai, Yinlong Guo, Kuiling Ding, Qian Peng, Xiaoming Wang
Summary: This study demonstrates the use of binuclear metal complexes as catalysts to switch the selectivity of 1,3-dienes from 4,3-regioselectivity to 1,4-hydroarylation with Z-stereoselectivity. The findings highlight the potential of binuclear catalysis in achieving new isomers that were previously inaccessible.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Fen You, Wenyu Shi, Xuyang Yan, Xiaoyu Wang, Xiaochao Shi
Summary: The reliance on fossil resources and the accumulation of polymeric materials in the environment pose significant challenges to sustainable society. Utilizing renewable monomers for polymeric materials has gained attention, and terpenes are a commonly used bio-based monomer. This review focuses on the rare-earth metal catalyzed polymerization of bio-based conjugated dienes from terpene-derived compounds, and discusses the future directions for modifying these bio-based conjugated dienes.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Applied
Ze-Jian Xue, Meng-Yao Li, Bin-Bin Zhu, Zhi-Tao He, Chen-Guo Feng, Guo-Qiang Lin
Summary: The palladium-catalyzed cross-coupling of ortho-vinyl aromatic bromides and olefins using a controllable 1,4-palladium migration/Heck cascade protocol is a mild, efficient, and highly stereoselective method for the synthesis of trisubstituted 1,3-dienes, especially triaryl-substituted ones.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Applied
Haixia Zhao, Yuchen Jiang, Tongqing Weng, Yongjia Shang, Jian Wang
Summary: A three component construction of conjugated 1,3-dienes bearing oxindoles or isoquinolinediones from alkenylated aryl iodides, allenes and diazo compounds via a palladium catalyzed sequential alkene/allene/carbenoid insertion reaction was developed. Three C-C bonds were formed in high order, offering access to multi-substituted dienes in high yields and up to > 20:1 E/Z selectivities. The reaction features excellent functional groups tolerance under mild conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Haoxiang Zhang, Lin Guo, Chao Yang, Wujiong Xia
Summary: A facile electrochemical alkylation reaction has been developed for the synthesis of trans-olefins through the reaction of buta-1,3-diene derivatives with alkyl halides. This method offers significant advantages such as simplicity, mild conditions, and scalability.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Fengjie Huang, Zhidao Huang, Guixia Liu, Zheng Huang
Summary: A trans-semihydrogenation of 1,3-enynes with ethanol was developed using a new (PCN)Ir complex and tBuNH2 as catalysts, providing an efficient synthesis of unsymmetrical (E,E)-1,4-diarylbutadienes.
Article
Biochemical Research Methods
Ekaterina S. Starnovskaya, Dmitry S. Kopchuk, Yaroslav K. Shtaitz, Maria Savchuk, Igor L. Nikonov, Ilya N. Egorov, Grigory Zyryanov, Vladimir L. Rusinov, Oleg N. Chupakhin
Summary: A convenient synthetic approach to asymmetrically functionalized 1,3-di(2-pyridyl)benzenes starting from 3-(3-bromophenyl)-1,2,4-triazines using sequential aza-Diels-Alder reactions and Stille cross-coupling is reported in this study, with the photophysical properties of the obtained compounds being studied.
JOURNAL OF FLUORESCENCE
(2022)
Article
Chemistry, Inorganic & Nuclear
Fen You, Jingjing Zhai, Yat-Ming So, Xiaochao Shi
Summary: A series of rare-earth metal alkyl complexes were successfully synthesized in this study, which could efficiently catalyze the living polymerization of isoprene and beta-myrcene with high cis-1,4-selectivity. Moreover, the complexes could also promote the polymerization of butadiene and its copolymerization with isoprene to produce copolymers with high cis-1,4-selectivity and narrow polydispersity.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Hui Liu, Xiaochao Shi
Summary: A series of new phosphasalalen pro-ligands were synthesized and found to catalyze the ring-opening polymerization reaction efficiently, displaying special effects and maintaining binuclear structures.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Suting Xu, Jixing Wang, Jingjing Zhai, Fei Wang, Li Pan, Xiaochao Shi
Summary: The study reported the preparation of novel imidazoline-2-imine functionalized fluorenyl ligands with an ethylene bridge and their corresponding rare-earth metal complexes. The rare-earth metal complexes showed high efficiency in promoting the syndiotactic polymerization of ortho-methoxystyrene, achieving a high level of isotacticity. Additionally, the activation effect of the polar groups via sigma-pi chelation of the methoxy and vinyl groups was investigated.
Article
Chemistry, Inorganic & Nuclear
Fen You, Suting Xu, Jixing Wang, Jingjing Zhai, Fei Wang, Li Pan, Yat-Ming So, Xiaochao Shi
Summary: A simple method for accessing new derivatizable bulky-demanding OHF ligands has been developed, leading to the synthesis of a series of half-sandwich rare-earth metal complexes bearing the OHF ancillary ligands, which exhibit high catalytic activity for styrene (co)polymerization.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Jingjing Zhai, Fen You, Suting Xu, Ao Zhu, Xiaohui Kang, Yat-Ming So, Xiaochao Shi
Summary: A simple and efficient synthetic pathway was developed to prepare a new iminodibenzyl-based PNP pincer proligand, leading to the successful synthesis of a series of iminodibenzyl-PNP rare-earth-metal complexes. Among them, a yttrium complex exhibited high selectivity in the polymerization of 1,3-dienes.
INORGANIC CHEMISTRY
(2022)
Article
Polymer Science
Fen You, Xiaohui Kang, Masayoshi Nishiura, Jingjing Zhai, Suting Xu, Jixing Wang, Xiaochao Shi, Zhaomin Hou
Summary: This study reports the living and highly 3,4-isoselective polymerization of biobased monomer beta-farnesene using a phosphine-functionalized fluorenyl-ligated yttrium catalytic system. The coordination of the phosphine group plays a pivotal role in the regio- and stereoselectivity of the polymerization. Block copolymers with specific properties were successfully prepared. This research is important for reducing petrochemical dependency.
Review
Chemistry, Multidisciplinary
Fen You, Wenyu Shi, Xuyang Yan, Xiaoyu Wang, Xiaochao Shi
Summary: The reliance on fossil resources and the accumulation of polymeric materials in the environment pose significant challenges to sustainable society. Utilizing renewable monomers for polymeric materials has gained attention, and terpenes are a commonly used bio-based monomer. This review focuses on the rare-earth metal catalyzed polymerization of bio-based conjugated dienes from terpene-derived compounds, and discusses the future directions for modifying these bio-based conjugated dienes.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Polymer Science
Wenhui Ren, Fen You, Jingjing Zhai, Xiaohui Kang, Yat-Ming So, Xiaochao Shi
Summary: This study presents a single rare-earth metal catalyst that can promote the polymerization of isoprene and butadiene with unmatched stereoselectivity, resulting in polymers with different cis or trans structures. Moreover, the catalyst allows for the precise control of diblock and multiblock copolymers with differently stereoselective adjacent blocks. The mechanical properties of the produced block copolymers can be tailored by controlling the sequence length.
Article
Chemistry, Inorganic & Nuclear
Hui Liu, Fen You, Xiang Hu, Yanchen Huo, Xiaochao Shi
Summary: A family of rare-earth metal complexes with diverse chiral substituents were synthesized and exhibited high catalytic activity and heteroselectivity in ring-opening polymerization. The yttrium complexes showed higher activity and heteroselectivity, while the chiral substituents had slight influence on the reaction.
Article
Chemistry, Inorganic & Nuclear
Suting Xu, Yanchen Huo, Xiang Hu, Fei Wang, Li Pan, Xiaochao Shi
Summary: In this study, rare-earth metal complexes bearing tetrahydrofluorenyl ligands were synthesized and characterized. These complexes showed excellent catalytic activity for the polymerization of styrene and butadiene, resulting in diblock copolymers with highly syndiotactic polystyrene block and a 1,4-specific PBD block. The study also revealed the significant difference in reactivity ratios between butadiene and styrene, supporting the block structure of the copolymers. Morphology and mechanical properties of the selected diblock copolymer were investigated.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Fen You, Jixing Wang, Hui Liu, Xiaohui Kang, Xiaochao Shi
Summary: A series of rare-earth metal bis(alkyl) complexes were synthesized through protonolysis reactions of tris(aminobenzyl) complexes with phosphine-functionalized amidinated ligands. These complexes showed high catalytic activity for the polymerization of 1,3-conjugated dienes, resulting in highly 3,4-regular polymers with high molecular weight and narrow molecular weight distribution. The coordination of the diphenylphosphine group to the central metal was observed, which may serve as the true active species in the 3,4-selective polymerization of 1,3-conjugated dienes according to 31P NMR spectra and DFT calculation results.
DALTON TRANSACTIONS
(2023)
Article
Polymer Science
Hui Liu, Fen You, Wenyu Shi, Xiang Hu, Yat-Ming So, Xiaochao Shi
Summary: In this study, we developed a series of novel terpene-derived conjugated dienes and successfully achieved their highly selective polymerization, resulting in high-molecular-weight polymers with high glass transition temperatures and excellent thermal stability.
Article
Chemistry, Multidisciplinary
Yanchen Huo, Xiang Hu, Jixing Wang, Hongfan Hu, Xiaochao Shi
Summary: Amido-trihydroquinoline ligated rare-earth metal complexes have been synthesized and showed moderate catalytic activities for isoprene polymerization. The 2-Y-based catalytic system exhibited excellent control over the polymerization. The alkylaluminium exerted varying influence on the polymerization, and AIMe(3) significantly enhanced the reactivity and 1,4-selectivity. The active yttrium-polyisoprene species were successfully utilized for the polymerization of caprolactone and its copolymerization with isoprene, demonstrating the tunable modification of the copolymer's surface hydrophilicity, with higher content of hydrophilic PCL sequence resulting in lower WAC.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Wenhui Ren, Hui Liu, Fen You, Pengjuan Mao, Yat-Ming So, Xiaohui Kang, Xiaochao Shi
Summary: A family of rare-earth complexes with different pincer ligands have been synthesized and characterized for their ability to catalyze the polymerization of isoprene with different stereoselectivities. Density functional theory calculations revealed the key reason for the trans-stereoselective isoprene polymerization catalyzed by lutetium complex P-Lu.
DALTON TRANSACTIONS
(2021)