Article
Chemistry, Organic
Anurag Singh, Rahul K. Shukla, Chandra M. R. Volla
Summary: In this study, a novel Ru(II)-catalyzed non-oxidative [5+1] annulation reaction was developed to access biologically relevant chromene skeletons. The heteroatom on allene was found to control the regioselectivity of migratory insertion, and the reaction proceeded through a Ru-sigma-allyl pathway, which is unprecedented in C-H activation reactions with allenes. This sustainable protocol was carried out at room temperature without the use of any toxic metal oxidants. The synthetic utility of the method was demonstrated by late stage functionalization and modular synthesis of various natural product conjugates.
Article
Chemistry, Multidisciplinary
Kua-Fei Wei, Qing Liu, Guang Ma, Xiao-Lei Jiang, Xiu-Hong Zhu, Guang-Xin Ru, Wen-Bo Shen
Summary: A copper-catalyzed hetero Diels-Alder reaction of allenynes with cis diazenes has been developed to efficiently synthesize a diverse array of valuable polycyclic N-heterocycles. The reaction exhibits temperature control and stereocontrol, leading to the synthesis of tetracyclic pyrrolidines, pentacyclic triazepanes, and tricyclic pyrrolidines.
COMMUNICATIONS CHEMISTRY
(2023)
Article
Chemistry, Organic
Guo-Li Chai, En-Ze Yao, Rui-Hao Liu, Junbiao Chang
Summary: In this study, a new catalytic system was reported for the synthesis of N,N'-bicyclic pyrazolidine derivatives with high stereoselectivity. The reaction conditions are mild and efficient, with a broad substrate scope.
Article
Chemistry, Organic
Shuang-Hu Chen, Yu-Hang Miao, Guang-Jian Mei, Yuan-Zhao Hua, Shi-Kun Jia, Min-Can Wang
Summary: An atom-economical asymmetric [3 + 2] spiroannulation reaction has been developed for the synthesis of novel bispirocyclic compounds with biological activity via bimetallic cooperative catalysis.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Zhe Fan, Shao-Fei Ni, Jin-Yu Pang, Li-Ting Guo, Hao Yang, Ke Li, Cheng Ma, Ji-Kai Liu, Bin Wu, Jin-Ming Yang
Summary: A novel strategy for the formation of copper carbene and a Cu(I)-catalyzed cross-coupling protocol for the synthesis of 7-alkynyl cycloheptatrienes have been reported in this study.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Zhi-Kai Liu, Jia-Hao Zeng, Zhuang-Ping Zhan
Summary: A concise and useful method for synthesizing 3-substituted indole derivatives via a palladium-catalyzed reaction has been reported. The method showed moderate to good yields and demonstrated great potential for application through gram-scale experiments and diverse product transformations.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Yipeng Zhou, Hongwei Zhou, Jianfeng Xu
Summary: A highly selective [3+2] cycloaddition reaction was achieved using a chiral catalyst, resulting in the synthesis of enantioenriched bicyclic pyrazolidinones.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yadi Niu, Laiping Yao, Hongli Zhao, Xue Tang, Qian Zhao, Yuling Wu, Bo Han, Wei Huang, Gu Zhan
Summary: This study presents a new method for the asymmetric synthesis of spiroxindole cyclopentanes containing five stereocenters. The strategy demonstrated a broad substrate scope and high selectivity.
Article
Chemistry, Applied
Camille Van Wesemael, Nicolas Brach, Mihaela Gulea, Gaelle Blond
Summary: A series of 3-allenyl benzo[b]thiophenes were synthesized through a gold(I)-catalyzed domino reaction. The process involves a 5-endo-dig cyclization with C S bond formation and consecutive S-to-C propargyl migration via [3,3]-sigmatropic Claisen rearrangement. Various fused O-heterocycles can be obtained from a substrate bearing a 3-butynol moiety via intramolecular hydroalkoxylation. The gold-mediated 1,3-migration involving allenyl to propargyl rearrangement is also described.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Zhehui Liao, Jiantao Zhang, Tongxiang Cao, Shifa Zhu
Summary: A series of highly strained bicyclo[3.n.1]alkenones have been successfully synthesized with good-to-excellent enantioselectivities and moderate-to-good yields via copper-catalyzed formal [3+3] cycloaddition. The versatile chiral cycloadducts could be selectively converted into various valuable bridge systems, showing great potential for the construction of natural and bioactive compounds containing a [3.n.1] moiety.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Rui-Hao Liu, Guo-Li Chai, Xiao Wang, Hong-Yu Deng, Junbiao Chang
Summary: The asymmetric 1,3-dipolar cycloaddition reaction of beta-trifluoromethyl alpha,beta-unsaturated ketone with N,N'-cyclic azomethine imines was developed using a (R)-3,3'-(3,5-(CF3)2-C6H3)2-BINOL-boron complex catalyst. The reaction efficiently produces N,N'-bicyclic pyrazolidine derivatives with a stereogenic carbon center containing CF3 motifs in high yields and excellent diastereo- and enantioselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Hai-Tao Zhu, Chun-Miao Liang, Ting-Yan Li, Lin-Yan Li, Rui-Ling Zhang, Jun-Na Wang, Rui-Qing Qi, Jia-Min Zhang, Ruo-Han Yang, Yin-Qi Yang, An-Xi Zhou, Xiaojie Jin, Ni-Ni Zhou
Summary: A one-pot step-economic tandem process involving (5 + 2)-cycloaddition and Nazarov cyclization reactions has been developed for the synthesis of indanone-fused benzo[cd]azulenes. The reaction is highly regio- and stereoselective and enabled by dual silver and Bronsted acid catalysis, providing a new avenue for the construction of important bicyclo[5.3.0]decane skeletons.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Vinh Do Cao, Huiae Kim, Jaesung Kwak, Seewon Joung
Summary: We described the (3 + 2) cycloaddition reaction between endocyclic N-silyl enamines and N,N'-cyclic azomethine imines. This reaction utilized the versatile endocyclic N-silyl enamine intermediates obtained from the dearomative hydrosilylation of N-heteroarenes, and the tetracyclic pyrazolidinone structure was synthesized in a straightforward and atom-economical manner. We also discussed the potential origins of the different reactivity and endo/exo selectivity based on the structures of proposed transition states.
Article
Chemistry, Organic
Ke-Fan Wu, Dong-Ting Dai, Xin-Yue Sun, Yun-He Xu
Summary: A copper-catalyzed borylation of propargyl dichlorides was developed, leading to the formation of chloro-substituted allenyl-Bdan products in good yields under mild reaction conditions. The utilities of these products were examined through various derivatizations.
Article
Chemistry, Organic
Zhan-Cai Ma, Lin-Wen Wei, Yuan Huang
Summary: We have developed a highly efficient stereodivergent [4 + 2] annulation reaction using palladium catalysis to synthesize N-heterocycles with 1,3-nonadjacent stereogenic centers. The diastereoselectivity of the reaction is dependent on the polarity of solvents used. Additionally, good enantioselectivities were achieved by employing the chiral ligand Wingphos.
Article
Chemistry, Multidisciplinary
Juan Feng, Jiayi Shi, Lan Wei, Mingqing Liu, Zhiming Li, Yuanjing Xiao, Junliang Zhang
Summary: In this study, a highly regio- and diastereo-selective palladium/PC-Phos-catalyzed asymmetric Heck/Tsuji-Trost reaction was reported for the synthesis of various functionalized chiral hexahydroindoles with good yields and high enantioselectivity. The application of this reaction to the concise synthesis of (-)-alpha-Lycorane was demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ruihan Wang, Yidong Wang, Ruiqi Ding, Parker B. Staub, Christopher Z. Zhao, Peng Liu, Yi-Ming Wang
Summary: A newly-developed cationic cyclopentadienyliron dicarbonyl complex enables the conversion of propylene to its allylic C-C bond coupling products under catalytic conditions. This approach is also applicable to the allylic functionalization of simple alpha-olefins with distinctive branched selectivity. Experimental and computational studies reveal the allylic deprotonation of the metal-coordinated alkene as the turnover-limiting step and provide insights into the multifaceted roles of the newly designed ligand in promoting allylic C-H functionalization with enhanced reactivity and stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Ruiqi Ding, Yidong Wang, Yi-Ming Wang
Summary: We have developed a synthesis method for allenylic silyl ethers through the iron-catalyzed functionalization of C(sp(2))-H bonds. By using a cyclopentadienyliron dicarbonyl based catalyst and triisopropylsilyl triflate as a silylation agent, a variety of aryl aldehydes were successfully coupled to give 1,1-disubstituted allenylic triisopropylsilyl ethers in moderate to excellent yields as a single regioisomer. Lithium bistriflimide was found to be a critical additive in this transformation. The optimized protocol was scalable and the products could be further transformed into various unsaturated, polyfunctional derivatives.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Yin Yuan, Junfeng Yang, Junliang Zhang
Summary: In this study, a Cu-catalyzed enantioselective decarboxylative cyanation method via the merger of photocatalysis and electrochemistry was reported. This method provides an efficient and straightforward approach for decarboxylative coupling, eliminating the need for stoichiometric chemical oxidants or substrate prefunctionalization. Mechanistic insight on enantioselectivity control was obtained through DFT calculations.
Article
Chemistry, Multidisciplinary
Chun Ma, Yue Sun, Junfeng Yang, Hao Guo, Junliang Zhang
Summary: In this study, an efficient method for the catalytic synthesis of Troger's base analogues with nitrogen stereocenters was reported. The process involved palladium catalysis and the use of home-developed GF-Phos. The method allowed for the rapid construction of a new rigid cleft-like structure with both C and N stereogenic centers, exhibiting excellent efficiency and selectivity. Various applications as a chiral organocatalyst and metallic catalyst precursors were demonstrated, and DFT calculations revealed that NH center dot center dot center dot O hydrogen bonding and weak interaction between the substrate and ligand played crucial roles in achieving excellent enantioselectivity control.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Youshao Tu, Bing Xu, Qian Wang, Honglin Dong, Zhan-Ming Zhang, Junliang Zhang
Summary: In this work, we developed a highly enantioselective Pd/TY-Phos-catalyzed Heck/Tsuji-Trost reaction of o-bromophenols with various 1,3-dienes, allowing expedient access to chiral substituted 2,3-dihydrobenzofurans. This reaction features excellent regio-and enantiocontrol, high functional group tolerance, and easy scalability. More importantly, the demonstration of this method as a highly valuable tool for the construction of optically pure natural products (R)-tremetone and fomannoxin is highlighted.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Sarah G. Scrivener, Yidong Wang, Yi-Ming Wang
Summary: The iron-catalyzed coupling of alkenes and enones through allylic C(sp3)-H functionalization is achieved using a cyclopentadienyliron(II) dicarbonyl catalyst and simple alkene substrates. The reaction generates catalytic allyliron intermediates for 1,4-addition to chalcones and other conjugated enones. Mild, functional group-tolerant conditions are facilitated by the use of 2,4,6-collidine as the base and a combination of triisopropylsilyl triflate and LiNTf2 as Lewis acids. Both electronically unactivated alkenes and allylbenzene derivatives, as well as enones with various substituents, can be employed as pronucleophilic coupling partners.
Article
Multidisciplinary Sciences
Shiquan Gao, Chen Wang, Junfeng Yang, Junliang Zhang
Summary: In this study, an enantioselective intramolecular reductive coupling of enynes was achieved via the combination of electrochemistry and cobalt catalysis. The transition-metal catalyzed asymmetric cyclization of 1,6-enynes has been widely used for the construction of carbocycles and heterocycles, but examples under electrochemical conditions are rare. We report a Co-catalyzed enantioselective intramolecular reductive coupling of enynes using H2O as the hydride source, which provides good yields with high regio- and enantioselectivities. This study represents a rare progress on the cobalt-catalyzed enantioselective transformation via electrochemistry with a general substrate scope, and DFT studies suggest the possible reaction pathways.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Li-Ming Zhang, Wenjun Luo, Jiangzhen Fu, Yu Liu, Junliang Zhang
Summary: A newly developed PNP-type W-Phos ligand showed a unique effect on the catalytic asymmetric addition of reactive Grignard reagents to ketimines. This enabled a Cu(I)-catalyzed asymmetric alkylation reaction of N-sulfonyl ketimines, resulting in the formation of optically active α-tertiary amines with high enantioselectivities.
Article
Multidisciplinary Sciences
Jie Han, Siyuan Liu, Huanan Wang, Jie Wang, Hui Qian, Zhiming Li, Shengming Ma, Junliang Zhang
Summary: The 13-H elimination is a crucial step in the carbon-palladium bond quenching for the Heck reaction and has been a challenge to control enantioselectivity. Here, we developed a concise and efficient method to construct chiral allenes from fully substituted enol triflates through enantioselective 13-H elimination of alkenyl palladium species under mild conditions. The identified Xu-Phos catalysts play a crucial role in chemoselectivity and enantioselectivity. Multiple linear regression analysis shows the significance of steric effect on enantioselectivity. DFT calculations propose an intramolecular base-assisted deprotonation mechanism for this progress, and energy decomposition analysis suggests that the difference in electrostatic energy of the transition states dominates the stereoselectivity.
Article
Chemistry, Multidisciplinary
Dongdong Li, Chaoren Shen, Zhiyao Si, Lu Liu
Summary: A novel Pd-catalyzed fluorinative bifunctionalization of aziridines and azetidines was achieved via regioselective C-C and C-F bond cleavage of gem-difluorocyclopropanes, leading to various ss,ss'-bisfluorinated amines and ss,gamma-bisfluorinated amines in 100% atom economy for the first time.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Qiang Wang, Shuaijie Wu, Yi-Dong Wang, Jing Sun, Ying Han, Chao-Guo Yan, Lei Wang
Summary: Here, a new and efficient strategy for the synthesis of alkenyl sulfoxides is reported. The method involves the transition metal-free C-S cross-coupling reaction between sulfenate anions and alkenylsulfonium salts. The in situ generation of sulfenate anions from beta-sulfinyl esters under mild conditions provides an effective approach for the synthesis of diverse alkenyl sulfoxides in moderate to good yields.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Jiafeng He, Xun-Shen Liu, Mingjia Li, Shaoting Peng, Zhi-Yao Si, Lu Liu
Summary: A highly stereoselective chalcogenide ylide formation/Smiles rearrangement reaction of diaryl thioether/selenoethers and triazoles catalyzed by Rh(ii) was successfully developed, providing an efficient strategy for constructing trisubstituted acyclic vinyl sulfides/selenides. The key features of this protocol include simple operation, readily available starting materials, atom economy, broad substrate scope, and convenient transformation of products.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Review
Chemistry, Multidisciplinary
Bing Xu, Quanpu Wang, Chao Fang, Zhan-Ming Zhang, Junliang Zhang
Summary: This review summarizes the latest advancements in enantioselective palladium-catalyzed cyclization reactions over the past eleven years. The review is organized into thirteen sections based on the different types of transformations involved. Chiral palladium catalysts have shown outstanding features in promoting a plethora of enantioselective cyclization reactions, providing convenient access to structurally diverse chiral carbo- and hetero-cycles.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Zhi-Mao Zhang, Junliang Zhang, Quan Cai
Summary: In this study, seven pentacyclic 19-nor-clerodane diterpenoids were collectively synthesized using an asymmetric reaction. A key feature of the synthesis was the generation of a versatile intermediate through late-stage oxidation state adjustments. This study provides a concise and efficient synthetic route for these compounds.
