Article
Chemistry, Organic
Shiyu Xiang, Taotao Lu, Junjun Liu, Qingyang Zhao
Summary: An unprecedented redox transformation of β-sulfinyl esters to generate sulfinate anions has been discovered, enabling the asymmetric sulfonylation of vinylidene o-quinone methides and providing various sulfone-based axially chiral styrenes with excellent enantioselectivities.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Shi-Hui He, Guang-Le Chen, Xing-Yu Gong, Gui-Zhen Ao, Feng Liu
Summary: In this study, a redox-neutral and mild approach for radical sulfinylation of redox-active esters via dual photoredox and copper catalysis was developed, leading to a series of functionalized sulfoxides. The reaction demonstrated broad substrate scope and high compatibility with various functional groups. The practicality, scalability, and potential for late-stage modification of bioactive pharmaceuticals make this chemistry highly valuable.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Xuefeng Wang, Yulian Tang, Shengqing Ye, Jun Zhang, Yunyan Kuang, Jie Wu
Summary: A photocatalyzed transformation from sulfinic acids to sulfoxides under visible-light irradiation in the presence of N-heterocyclic carbene has been developed. Various alkyl groups from four-substituted Hantzsch esters or Meyer nitriles are smoothly converted to the corresponding sulfoxides through a radical coupling pathway in the presence of 1,1-carbonyldiimidazole. This method provides an alternative route for sulfoxide synthesis without relying on the oxidation of sulfides.
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
Wen Liu, Yan Zhang, Shuya Xing, Huilin Lan, Xinrui Chen, Ying Bai, Xinxin Shao
Summary: beta-Trifluorosulfinylesters were developed as novel reagents for direct trifluoromethylthiolation and trifluoromethylsulfinylation reactions. These reagents could be easily prepared in three steps without column purification, using inexpensive commercially available starting materials. The switchable reactivity of the reagents was controlled by different activators, with the formation of fluorinated sulfenate anions under basic conditions and fluorinated sulfonium salts under the presence of Tf2O. The fluorinated sulfonium salts served as electrophilic synthons for transition-metal-free C-H trifluoromethylthiolation of electron-rich arenes and alkenes.
ORGANIC CHEMISTRY FRONTIERS
(2023)
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
Biao Zhang, Junhao Ruan, Daniel Seidel, Weijie Chen
Summary: Unprotected cis-2,3-diarylpiperidines are synthesized through a palladium-catalyzed cross-coupling reaction between aryl halides and endocyclic 1-azaallyl anions. These intermediates are generated in situ by the deprotonation of 2-aryl-1-piperideines, precursors that are readily prepared from simple piperidines. An asymmetric version of this reaction provides products with moderate to good yields and enantioselectivities when using (2R, 3R)-iPr-BI-DIME as the ligand. This study expands the synthetic utility of endocyclic 1-azaallyl anions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Taiga Yurino, Sunaho Saito, Mizuki Ichihashi, Takeshi Ohkuma
Summary: A Pd(OAc)(2)/P(OPh)(3) combination catalyst was used for the Tsuji-Trost-type allylic amination under aerobic conditions, and it was found that the reaction proceeded efficiently only when allylic phosphates were employed as electrophiles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Shengzu Duan, Guogang Deng, Yujin Zi, Xiaomei Wu, Xun Tian, Zhengfen Liu, Minyan Li, Hongbin Zhang, Xiaodong Yang, Patrick J. Walsh
Summary: This study introduces a unique enantioselective nickel-catalyzed vinylation method for the synthesis of diverse vinyl aryl methyl amines and enantioenriched 1,3-diamine derivatives, which are frequently found in natural products and medications. The success of this method relies on a Ni/chiraphos catalyst system and a less reducing 2-azaallyl anion, enabling an anionic vinylation route over a background radical reaction. Scalability and synthetic potential of this method are confirmed through a telescoped gram scale synthesis and product derivatization study.
Review
Chemistry, Organic
Fumito Saito
Summary: This article reviews the significant advances in sulfenate protocols, including alkylation and arylation, and provides future directions for research in this field.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Jiateng Wang, Mengxia Liu, Yue Zhang, Gehua Bi, Yi Zhao, Kai Yang, Xin Huang
Summary: A switchable and benign protocol has been developed for the chemo-selective synthesis of sulfoxides and alpha-alkoxy-beta-ketothioethers. By regulating the reaction temperature, various thiophenols and alkenes/alkynes were found to be compatible for achieving the target compounds in medium to high yields. In particular, methanol not only acted as a solvent but also participated in the reaction process as a hydrogen donor. The study also demonstrated that Selectfluor is an efficient multifunctional reagent in the reaction system.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Lei Wang, Shuaijie Wu, Shuting Zhang, Qianqian Hu, Qiang Wang, Jing Sun, Ying Han, Chao-Guo Yan
Summary: A highly efficient palladium-catalyzed allenamide allylic alkylation of sulfenate anions under mild conditions is demonstrated, providing a practical protocol to access various sulfoxide-containing heterocyclic compounds. The transformation features a broad substrate scope, good functional group tolerance, easy scalability, and convenient synthetic transformation.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Mizzanoor Rahaman, M. Shahnawaz Ali, Khorshada Jahan, Damon Hinz, Jawad Bin Belayet, Ryan Majinski, M. Mahmun Hossain
Summary: The study investigated the reactions of carbonyl compounds and ethyl diazoacetate in the presence of a Bronsted acid catalyst, resulting in the synthesis of a variety of 3-oxo-esters through 1,2-aryl/alkyl/hydride shift. Different types of ketones produced different products, with aryl-methyl ketones only yielding aryl-migrated products. Identification of two inseparable migrated products in diaryl ketones was confirmed using two-dimensional NMR spectroscopy.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zhangjin Pan, Wenbo Li, Shuai Zhu, Feng Liu, Hai-Hong Wu, Junliang Zhang
Summary: An efficient Pd-catalyzed enantioselective intermolecular alpha-arylation reaction of alpha-alkyl-alpha-aryl disubstituted aldehydes with aryl bromides is reported here, providing chiral aldehydes bearing an alpha-all-carbon quaternary stereocenter in moderate to good yields with good enantioselectivity in most cases. A pair of enantiomers could be easily prepared by exchanging the aryl groups of aldehyde and aryl bromide using the same ligand.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Baixue Liu, Peng Liu, Xue Wang, Feng Feng, Zhen Wang, Wenqiang Yang
Summary: A general method for the gram-scale enantioselective synthesis of P-stereogenic cyclic phosphine oxides has been developed using copper-catalyzed dynamic kinetic resolution, leading to high yields and high enantioselectivities. The resulting products can be easily reduced to obtain useful P(III)-stereogenic cyclic phosphines. A proposed mechanism involves the unusual rapid racemization of SPOs.
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
Yong Wang, Yuxuan Li, Lei Wang, Shengtao Ding, Lijuan Song, Xinhao Zhang, Yun-Dong Wu, Jianwei Sun
Summary: In this study, a new method for efficient construction of gem-diboryl compounds with hetero-substituted carbon centers was developed. This method involves the alpha-dihydroboration of heteroalkynes and is a practical and atom-economic alternative to the conventional multistep synthetic strategy.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(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
Shuting Zhang, Shuaijie Wu, Qiang Wang, Shiji Xu, Ying Han, Chao-Guo Yan, Junliang Zhang, Lei Wang
Summary: This article reports the first palladium-catalyzed asymmetric alleneamination of beta,gamma-unsaturated hydrazones with propargylic acetates. The reaction enables the efficient installation of various multisubstituted allene groups onto dihydropyrazoles in good yields with excellent enantioselectivities. The salient features of this reaction include readily available starting materials, a broad substrate scope, easy scale-up, mild reaction conditions, and versatile transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(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
Shuaijie Wu, Shuting Zhang, Jing Sun, Ying Han, Yidong Wang, Chao-Guo Yan, Lei Wang
Summary: A highly efficient Pd-catalyzed carboetherification reaction between beta,gamma-unsaturated ketoximes and propargylic acetates is demonstrated. This method provides a practical protocol for accessing 3,5-disubstituted and 3,5,5-trisubstituted isoxazolines with an allene moiety. The transformation features a broad substrate scope, good functional group tolerance, easy scale-up, versatile transformations, and applications in late-stage drug modification.
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
Chemistry, Organic
Min Gao, Yinqiang Wang, Shuaijie Wu, Feier Ni, Cangzhu Hu, Feifei Jin, Jing Sun, Ying Han, Lei Wang
Summary: In this study, a novel and efficient strategy for the synthesis of dihydropyrazoles was presented. The synthesis involved the Pd-catalyzed carboamination reaction of alkenyl hydrazones with aryl triflates, leading to the simultaneous formation of C-C and C-N bonds. This methodology offers a practical and efficient approach for the synthesis of diversely aryl substituted dihydropyrazoles in good yields.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Organic
Han Liu, Lei Wang, Jin-Tao Yu
Summary: Ring-fused polycyclic structures are commonly found in natural products and pharmaceutical molecules, making the construction of such structures from readily available substrates an important topic in organic synthesis. Recent achievements have shown efficient and simple approaches for the formation of functionalized ring-fused structures from alkene-based substrates through radical-triggered cascade reactions. This review summarizes the formation of ring-fused polycyclic structures with no less than 3 fused rings, including the corresponding mechanisms.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
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, Organic
Shiji Xu, Qiang Wang, Jing Sun, Ying Han, Weiming Hu, Lei Wang, Chao-Guo Yan
Summary: In this study, Pd/Cu-catalyzed cascade Heck-type reactions between alkenyl halides and terminal alkynes have been developed. This research provides an efficient atom-economical approach to access a variety of highly substituted pyrrolidines in moderate to good yields. This protocol features readily available substrates, broad substrate scope, easy scale-up, high selectivities, and versatile transformations.
ORGANIC & BIOMOLECULAR CHEMISTRY
(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, 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.
