Article
Chemistry, Applied
Gang Wang, Mingzhu Wei, Tianxiang Liu, Weiwei Jin, Yonghong Zhang, Bin Wang, Yu Xia, Chenjiang Liu
Summary: A palladium-catalyzed stereoselective intramolecular Heck dearomative of indoles with silyl termination has been developed. This method allows the synthesis of tetracyclic indoline derivatives containing silicon, using N-(2-bromobenzoyl)indoles and silylboronates as starting materials. The protocol shows a broad substrate scope and high yields, and can be scaled up as well as further transformed.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Linhong Zuo, Wusheng Guo
Summary: A Pd-catalyzed decarboxylative approach for the construction of 2-allyl-2,2-diarylacetaldehydes via a dearomative umpolung strategy is presented. The reaction is applicable to various cyclic carbonates or allylic acetates with different functional groups. The reaction can be scaled up to gram-scale without loss of efficiency. Control experiments suggest that the reaction proceeds through a palladium-catalyzed dearomative decarboxylation step followed by an umpolung nucleophilic attack.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Yuxuan Ye, Seoung-Tae Kim, Ryan P. King, Mu-Hyun Baik, Stephen L. Buchwald
Summary: Pd-catalyzed nucleophilic fluorination reactions are important for the synthesis of fluoroarenes and fluoroalkenes. However, the regioselectivity of these reactions is often poor, generating a mixture of difficult-to-separate regioisomeric products. In this study, the addition of a substoichiometric quantity of TESCF3 significantly improved the regioselectivity by diminishing the formation of LPd-cyclohexyne complexes through an unexpected dearomatization pathway involving nucleophilic attack from a trifluoromethyl anion (CF3-).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ren-Xiao Liang, Ling-Jie Song, Jin-Bo Lu, Wei-Yan Xu, Chao Ding, Yi-Xia Jia
Summary: The study presents a PdH-catalyzed enantioselective heteroarenyne cycloisomerization reaction and a classical enantioselective 1,5-enyne cycloisomerization of N-vinylpropiolamides, showcasing the synthesis of diverse chiral spiro and fused indoline derivatives as well as chiral 2-pyrrolones with good to excellent enantioselectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jia-Hao Xie, Chao Zheng, Shu-Li You
Summary: A novel Pd-catalyzed method for dearomative methoxyallylation of 3-nitroindoles with allyl carbonates has been developed, achieving high yields and diastereoselectivity. The method demonstrates good scalability and practicality with relatively low catalyst loading. Kinetic experiments suggest that the nucleophilic attack of the alkoxide anion is the rate-determining step in this reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yota Uwabe, Kei Muto, Junichiro Yamaguchi
Summary: The total synthesis of C11-oxygenated Cephalotaxus alkaloids, fortuneicyclidins A and B, and cephalotine B was achieved by Pd-catalyzed dearomative spirocyclization of bromofurans with N-tosylhydrazones, followed by acid-mediated tandem transformation. The concise synthesis of these compounds was completed through chemo-selective and catalytic functional group conversions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Sheng Zhang, Xiujuan Feng, Ming Bao
Summary: Transition-metal catalyzed multi-component reactions have attracted attention in organic and drug synthesis due to their simplicity, availability of raw materials, and lack of intermediate separation. Among these reactions, three-component processes have become effective organic procedures. This article reviews the development of benzylpalladium intermediates in the rapid construction of two new chemical bonds.
Article
Chemistry, Physical
Xiao-Qing Han, Lei Wang, Ping Yang, Jing-Yuan Liu, Wei-Yan Xu, Chao Zheng, Ren-Xiao Liang, Shu-Li You, Junliang Zhang, Yi-Xia Jia
Summary: A palladium-catalyzed intramolecular enantioselective Mizoroki-Heck reaction of naphthalenes has been developed, leading to the formation of a series of unique heterocyclic compounds with enantiomeric excess values retained. The reaction relies on the use of a chiral sulfonamide phosphine ligand to inhibit competitive and undesired reactions.
Article
Chemistry, Multidisciplinary
Dong Gao, Lei Jiao
Summary: This study presents an efficient method for constructing indoline structures with a C2-quaternary stereocenter and controlling the migrating group through aza-semipinacol rearrangement. It enables the divergent access to dearomatized indole derivatives with either a C3- or a C2-quaternary stereocenter.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Gang Liao, Tao Zhang, Liang Jin, Bing-Jie Wang, Cheng-Kai Xu, Yu Lan, Yu Zhao, Bing-Feng Shi
Summary: In this study, we investigated the directing ability of chalcogenoether motifs in Pd-catalyzed atroposelective C-H functionalization through experimental and DFT computational studies. The results showed that the thioether motif exhibited superior reactivity and enantioselectivity compared to the corresponding ether and selenoether. Notably, DFT calculations provided a predictive model for optimizing reaction conditions and interpreting the origin of enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Tohama B. Abdullah, Hayfa M. Jirjes, Ahmed S. Faihan, Ahmed S. M. Al-Janabi
Summary: This study synthesized seven picolylamine dithiocarbamate complexes of M(II) ions (CoII, NiII, CuII, PdII, ZnII, CdII, and HgII) and investigated their structural geometries and properties. The complexes showed a square planar or tetrahedral geometry formed by the coordination of the dithiocarbamate ligand through sulfur atoms. Surface structural analysis revealed nano-pattern properties, such as a nano-flower pattern in Cd(II) and Hg(II) complexes. The complexes exhibited remarkable antibacterial activity against both Gram-positive and Gram-negative bacteria.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Chemistry, Applied
Yilin Zhao, Xue Wang, Ru Yao, Chengwen Li, Zelin Xu, Liming Zhang, Guifang Han, Jingli Hou, Yangping Liu, Yuguang Song
Summary: In the presence of Fe(III) complex and Bipy ligand, CF3-containing spirocarbocycles were conveniently obtained in high yields (20-99%) with high regioselectivity through Iron-catalyzed trifluoromethylation of unactivated alkenes coupled with phenol dearomatizing spirocyclization.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Jeewani P. Ariyarathna, Nur-E Alom, Leo P. Roberts, Navdeep Kaur, Fan Wu, Wei Li
Summary: This study discloses practical strategies for the synthesis of morpholines and Claisen rearrangement products based on the divergent reactivity of a common halonium intermediate. By utilizing readily available alkenes in a Lewis acid-catalyzed halo-etherification process, exceptional regioselectivity is achieved for both activated and unactivated olefins. Additionally, a mechanistic probe reveals an interesting regiochemical kinetic resolution process.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Cosimo Boldrini, Syuzanna R. Harutyunyan
Summary: The Pd-catalyzed allylative dearomatisation of naphthyl halides using Grignard reagents is shown to be feasible, with high reactivity of the nucleophile allowing for fast reactions and low catalyst loading. A variety of successfully substituted compounds were produced, demonstrating a broad scope, including reactivity of five membered heteroaromatic compounds under similar conditions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Si-Yuan Liu, Zhi-Ming Li, Hao Guo, Jun-Liang Zhang
Summary: DFT computations were performed on Pd/Xiao-Phos-catalyzed asymmetric arylation of SPOs, presenting a modified mechanism involving tautomerization and arylation. Various tautomerization mechanisms were investigated, and the catalytic effect of base on this process was highlighted. Further computations revealed that oxidative addition is the enantioselectivity-determining step, with the difference in non-bonding interactions between Xiao-Phos and SPO parts considered as the origin of selectivity. This study provides deeper insights into the self-adaptive property of SadPhos ligands and offers valuable guidance for ligand design.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Ling Meng, Heyang Liu, Zhenyang Lin, Jun Wang
Summary: Highly efficient and straightforward access to enantioenriched five-membered ring-fused chromanones is achieved via [3+2]-cycloaddition. The reaction yields densely functionalized chiral cyclopenta[b]chromanones with high enantioselectivity and diastereoselectivity. The mechanism and selectivity of the reaction have been investigated.
Article
Chemistry, Multidisciplinary
Tong-Tong Liu, Jiaxin Chen, Xin-Lei Chen, Li Ma, Bing-Tao Guan, Zhenyang Lin, Zhang-Jie Shi
Summary: A new class of boryl radicals ligated by a cyclic CAAC is reported, featuring a large spin density on the boron center as ascertained by EPR spectroscopy and DFT calculations. Structural and computational analyses revealed that stability of these radicals is assisted by the CAAC ligand and a weak but significant B(III)Br-B(II) interaction, suggesting a cooperative avenue for stabilization of boryl radicals. Two-electron reduction of these radicals provides C-H insertion products via a borylene intermediate.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Tong-Tong Liu, Jiaxin Chen, Bing-Tao Guan, Zhenyang Lin, Zhang-Jie Shi
Summary: Derived from structurally similar precursors, two different azidodiboranes underwent distinct aryl migration reactions triggered by different boron-boron separation distances. A shorter boron-boron distance led to heterolateral aryl migration and the formation of a seven-membered azadiborepin, while a longer boron-boron distance resulted in a stable bis-azidoborane scaffold. The pyrolysis of the bis-azidoborane led to the formation of an eight-membered oxazadiborocine through homolateral aryl migration and subsequent [3+2] cycloaddition. Density functional theory (DFT) calculations revealed that the boron-boron separation distances were the intrinsic factors driving the distinct migrations.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Wing Hei Marco Wong, Xueying Guo, Hok Tsun Chan, Tilong Yang, Zhenyang Lin
Summary: Heavier main-group element-catalyzed reactions have become an increasingly attractive tool for mimicking the behaviors of transition metal catalysts. The Bi-catalyzed synthesis of aryl sulfonyl fluorides reported by Magre and Cornella exhibits the ability of hypervalent coordination of the Bi(III) center and the high polarity of the Bi-Ph bond, allowing the heavier main-group element to resemble the transition metal in ligand association and dissociation flexibility. Additionally, the migrating Ph group's available pi electron pair stabilizes the SO2 insertion transition state by maintaining interaction with the Bi(III) center during migration.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Xin Xu, Zhenyang Lin
Summary: A mild synthetic method for transforming aromatic carbon-oxygen (C-O) bonds into useful molecules was reported. The method involved the use of a carbene complex to catalyze the asymmetric ring-opening reaction of dinaphthofuran with PhMgCl at room temperature. Density functional theory (DFT) calculations were performed to investigate the detailed mechanism, revealing a novel pathway involving Mg(II)-O coordination, phenyl nucleophile migration, and oxidative addition of a C-O bond to Ni(0). Insights into the role of the chiral NHC ligand in inducing enantioselectivity were also obtained.
Article
Chemistry, Multidisciplinary
Junyi Wang, Shuai Zhu, Wangyang Ma, Zhenyang Lin, Qing Ye
Summary: BN-butafulvenes, mono-BN isosteres of butafulvene and highly strained isomers of azaborines and B-amino boroles, have been synthesized via hydrolysis of the urana-borabicyclic complexes obtained from the reactions of bis(alkynyl)boranes with an uranacyclopropene complex. Their 4-dimethylaminopyridine (DMAP) adducts can further isomerize to 1,2,4,6-multisubstituted BN-9,1-naphthalenes. Both NMR reaction monitoring and theoretical calculations point to a reaction mechanism involving dearomative insertion of DMAP followed by two consecutive 1,2-hydrogen shifts. The photophysical studies of the highly substituted BN-9,1-naphthalenes reveal a notable redshift in both the UV/Vis absorption and emission spectra. The (TD)-DFT calculations corroborate the experimental data, suggesting that the strong pi-donating amino substitution at the 1- and/or 6-positions destabilizes the HOMO, and thus leading to a notable decrease of the HOMO-LUMO gap.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Shuxuan Liu, Ka Lok Chan, Zhenyang Lin, Jianwei Sun
Summary: This article reports the use of extended quinone methides with carbonyl and methide units distributed across two different rings as intermediates for asymmetric synthesis. By using suitable chiral phosphoric acids, the first asymmetric process involving such intermediates was achieved. These processes provide a rapid and highly enantioselective access to previously less accessible remotely chiral naphthols and naphthylamines. Control experiments and DFT calculations reveal important insights into the reaction mechanism, which likely involves the role of two phosphoric acid molecules in the enantiodetermining transition states. This work serves as a proof of concept for the exploitation of new types of extended quinone methides as versatile intermediates for asymmetric synthesis, offering a new platform for the efficient construction of remote benzylic stereogenic centers of aromatic compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Kalok Chan, Long Thanh Ta, Yong Huang, Haibin Su, Zhenyang Lin
Summary: In this study, a simple molecular representation method was developed using machine learning and artificial intelligence techniques to predict rate constants of aryl bromides in palladium-catalyzed Sonogashira coupling reactions. The results demonstrate the importance of incorporating domain knowledge into machine learning for improved data analysis.
Article
Chemistry, Multidisciplinary
Xiaonan Li, Tilong Yang, Jiayuan Li, Xiang Li, Pinhong Chen, Zhenyang Lin, Guosheng Liu
Summary: Palladium-catalyzed remote 1,n-dioxygenation (n = 4) of internal alkenes using engineered pyridine-oxazoline (Pyox) ligands is reported. The reactions exhibit high regio- and enantioselectivity, and have a broad substrate scope, providing optically pure 1,n-diol acetates as key synthons for bioactive molecules. Experimental and theoretical studies reveal that the regioselectivity is controlled by the reactivity disparity of two allylic C-H bonds, with the first palladium migration step being the regioselectivity-determining step facilitated by modified phenyl-substituted Pyox ligands.
Article
Chemistry, Inorganic & Nuclear
Rain Ng, Shun-Cheung Cheng, Ka-Lok Chan, Cheuk-Pui Leung, Wai-Man Cheung, Herman H. -Y. Sung, Hung Kay Lee, Chi-Chiu Ko, Ian D. Williams, Zhenyang Lin, Wa-Hung Leung
Summary: In this study, iridium complexes containing a bis-cyclometalated tripodal CANAC ligand were synthesized and their redox property and reactivity were investigated. Various iridium complexes were successfully obtained through different reactions, and their structures and properties were further studied. The results highlighted the crucial role of the CANAC ligand in stabilizing high-valent iridium.
Article
Chemistry, Multidisciplinary
Masahiro Yamamoto, Wing Chun Chan, Zhenyang Lin, Makoto Yamashita
Summary: The reaction between tetra(o-tolyl)diborane(4) and organic azides yields three different compounds, diborylamines, diboryltriazenes, and B-2-hexazenes with a bicyclic B2N6 ring system. Aryl azides react to form diborylamines, while 1 equiv. of alkyl azides results in diboryltriazenes. Excess primary alkyl azide leads to the formation of new heterocyclic B-2-hexazenes. Control experiments and DFT calculations support the general reaction mechanism via diboryltriazenes to explain the formation of the B2N6 structure. The B-2-hexazenes exhibit strong fluorescence with a high fluorescent quantum yield of up to 96%.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Wenlong Sun, Chi-Ming Au, Ka-Wa Wong, Ka Lok Chan, Cheuk Kit Ngai, Hung Kay Lee, Zhenyang Lin, Wing-Yiu Yu
Summary: Directarene C-H functionalization by amidyl radicals has made significant progress for arylamides synthesis. Photocatalytic protocols can easily generate amidyl radicals under mild conditions, but designing catalysts with earth-abundant Fe complexes for C-H amidation is an attractive approach for controlling selectivity. However, the preference for high-spin configuration makes it challenging to design robust Fe catalysts for C-H amidation.
Article
Chemistry, Physical
Yongheng Jia, Ruichen Li, Yang Zhou, Shenghe Zhao, Hui Yu, Jianpu Wang, Zhenyang Lin, Haibin Su, Ni Zhao
Summary: Perovskite light-emitting diodes (PeLEDs) based on 3D mixed Br-Cl compositions exhibit good color stability and efficiency in the sky-blue range, but suffer from a significant performance decay in the deep-blue emission. This decay is mainly attributed to the poor morphology of the emissive layer. By combining theoretical and experimental approaches, it is discovered that the exchange of halide ions in lead complexes drives the precipitation of CsCl, resulting in low solubility at high Cl/Br ratios and inadequate perovskite film coverage. A metastable dissolution strategy is proposed, leading to deep-blue PeLEDs with a record high EQE of 4% and excellent spectral stability.
Article
Chemistry, Multidisciplinary
Zhongming Cheng, Tilong Yang, Can Li, Yunshun Deng, Fangjia Zhang, Pinhong Chen, Zhenyang Lin, Shengming Ma, Guosheng Liu
Summary: This study presents a copper-catalyzed radical relay strategy for the site-selective cyanation of sp(2) C-H bonds in allenes. The reactions show broad substrate scope and remarkable functional group compatibility under mild conditions. The site-selectivity is attributed to the unique pocket created by the Cu-bound nitrogen-centered radical and the crucial hydrogen bonding between the fluoride and the hydrogen atom. Late-stage functionalization of drug-like bioactive molecules containing an allene motif becomes feasible.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Jiao Jiao, Pei He, Tilong Yang, Tingwei Zhang, Linghua Wang, Tian Han, Yong Nie, Zhenyang Lin, Pengfei Li
Summary: An asymmetric synthesis of chiral metallacarboranes using a traceless chiral N-tertbutylsulfinamide auxiliary is reported. Investigations reveal a stereospecific SN2-type reaction mechanism, providing a new pathway for the preparation of chiral metallacarboranes and related compounds.
ORGANIC CHEMISTRY FRONTIERS
(2023)