Article
Multidisciplinary Sciences
Yao Tang, Yu Wang, Qingkai Yuan, Sai Zhang, Jia-Yin Wang, Shengzhou Jin, Ting Xu, Junyi Pan, Kazimierz Surowiec, Guigen Li
Summary: There have been four methods documented in literature and textbooks for chirality control, including the use of chiral auxiliaries, reagents, solvents, and catalysts. This report presents a new type of asymmetric control, namely asymmetric catalysis via chiral aggregates, which is not classified under the aforementioned methods. The strategy involves the catalytic asymmetric dihydroxylation reaction of olefins using chiral ligands that aggregate in aggregation-induced emission systems. The work shows enhanced chiral induction by changing the ratios of the cosolvents tetrahydrofuran and H2O.
Editorial Material
Chemistry, Multidisciplinary
Bing Fang, Yixuan Li, Fazheng Ren
Summary: In a recent Nature paper, Xu et al. reported the synthesis of chiral Au nanoparticles with the highest g-factor value. These chiral nanoparticles can regulate immune cell maturation, opening up the possibility of using nano scale chirality as an adjuvant for vaccines.
Article
Chemistry, Physical
Jian-Hua Liu, Qing Zhou, Yao Lin, Zhu-Lian Wu, Tian Cai, Wei Wen, Yan-Min Huang, Qi-Xiang Guo
Summary: In this study, a highly efficient atom-economic asymmetric alpha-allylation method using chiral-aldehyde/palladium catalyst was reported. This method enables the asymmetric alpha-allylation of different 1,3-dienes and allenes with N-unprotected amino acid esters, leading to the synthesis of alpha,alpha-disubstituted chiral alpha-amino acid esters with high efficiency, good yields, and stereoselectivities. No N-allylation byproducts were observed in these reactions. Two reaction models were proposed based on mechanistic control experiments. Overall, this work demonstrates a new approach for preparing structurally diverse chiral amino acids and provides insights for developing chiral-aldehyde catalytic systems.
Article
Chemistry, Organic
Brigita Mudrakova, Renata Marcia de Figueiredo, Jean-Marc Campagne, Radovan Sebesta
Summary: We describe a stereoselective tandem reaction involving the asymmetric conjugate addition of dialkylzinc reagents to unsaturated acylimidazoles followed by trapping of the intermediate zinc enolate with carbocations. Chiral NHC ligands were used to generate chiral zinc enolates with high enantiomeric purities, which were then reacted with highly electrophilic onium compounds to yield densely substituted acylimidazoles. DFT calculations provided insights into the reactivity of the zinc enolates derived from acylimidazoles and allowed comparison with metal enolates obtained from other conjugate addition reactions.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yuki Saito, Shu Kobayashi
Summary: The application of heterogeneous catalysts in continuous-flow enantioselective hydroacylation reactions was studied. Catalysts were prepared by mixing supports and rhodium complexes, and showed excellent activity and enantioselectivity. Under optimized conditions, the catalysts exhibited high turnover numbers and could be applied to various substrates. Furthermore, sequential-flow reactions with other heterogeneous catalysts were demonstrated for the synthesis of biologically active molecules and functional materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yan-Bo Li, Hu Tian, Shuai Zhang, Jun-Zhao Xiao, Liang Yin
Summary: In this study, a copper(I)-catalyzed reaction of diarylphosphines and O-benzoyl hydroxylamines was developed, leading to the synthesis of aminophosphinites and P-chiral aminophosphinites. The reaction mechanism was proposed and further transformation to P-chiral phosphines was achieved.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Hsien-Liang Cho, Chien-Chen Lai, Yi-Hung Liu, Hsiu-Fu Hsu, Shie-Ming Peng, Sheng-Hsien Chiu
Summary: This paper reports the insertion of Pd(II) into an initially achiral rotaxane, resulting in two chiral metallorotaxanes. Chiral additives and chiral TRISPHAT counteranions were used to confirm the existence of chirality and resolve the enantiomers of the C-2-symmetrical N-heterocyclic carbene complex.
Review
Chemistry, Applied
Giovanni Maria Fusi, Silvia Gazzola, Umberto Piarulli
Summary: Transition metal chiral catalysts can have metal stereocenters in different coordination geometries, with stability achieved through the use of multidentate ligands or cyclopentadienyl anions to prevent decomplexation and recomplexation of labile ligands, allowing for highly enantioselective reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Junwen Wang, Jun Li, Yan Wang, Sisi He, Hengzhi You, Fen -Er Chen
Summary: In this study, a polymer-supported chiral heterogeneous copper catalyst was reported, which demonstrated high reactivity and enantioselectivity in asymmetric conjugate addition reactions.
Article
Chemistry, Applied
Ramon de la Serna, Joaquin Perez-Pariente, Luis Gomez-Hortigueela
Summary: In this study, the asymmetric catalytic activity of GTM-3 chiral zeolite in the ring-opening reaction of trans-stilbene oxide using alcohols as nucleophiles was systematically explored. The results showed that a proper chiral host-guest size match is crucial for the chiral manifestation of the zeolite catalyst. Additionally, secondary alcohols with larger size exhibited higher enantioselectivity than their linear counterparts. Furthermore, variation of reaction conditions, such as the concentration of the epoxide and reaction temperature, could greatly influence the enantioselectivity and selectivity of the reaction.
Review
Chemistry, Multidisciplinary
Josep Mas-Rosello, Ana G. Herraiz, Benoit Audic, Aragorn Laverny, Nicolai Cramer
Summary: The development of new chiral ligands is crucial for stereocontrol in metal-catalyzed reactions, especially with the increasing demand for bioactive molecules as single enantiomers. The successful application of Cp-X ligands in metal-catalyzed transformations allows access to valuable chiral molecules, with critical comparisons of existing ligand families and discussion of future research directions for further enhancing their performance and application in enantioselective catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Donglei Wang, Ying-Bo Shao, Yunrong Chen, Xiao-Song Xue, Xiaoyu Yang
Summary: An efficient method for the asymmetric synthesis of planar-chiral macrocycles (paracyclophanes) has been developed using chiral phosphoric acid catalysis for enantioselective electrophilic aromatic aminations with azodicarboxylates. This method allows for the synthesis of a wide range of chiral macrocycles with varying ring sizes and functional groups, achieving high yields and enantioselectivities. The mechanism and origins of the stereoselectivities of these reactions were investigated through experimental studies and computational calculations. Preliminary utilization of the planar-chiral macrocycle as a chiral organocatalyst demonstrated the potential applications of these novel chiral skeletons.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Jumpei Hirose, Takumi Wakikawa, Shun Satake, Masahiro Kojima, Manabu Hatano, Kazuaki Ishihara, Tatsuhiko Yoshino, Shigeki Matsunaga
Summary: The enantioselective intramolecular oxyamination of unsaturated alkoxyamines was achieved using a hybrid catalytic system consisting of Cp*Rh-III/chiral disulfonate/CuOAc, leading to tetrahydrofuran derivatives with a tetrasubstituted chiral center in high enantioselectivity. The use of a sterically hindered chiral disulfonate and a Cu additive was crucial for the success of the reaction.
Article
Chemistry, Multidisciplinary
Ge Yang, Wenwen Shi, Yunyang Qian, Xiao Zheng, Zheng Meng, Hai-Long Jiang
Summary: This study successfully achieved heterogeneous enantioselective catalysis by modulating the chiral microenvironment around Lewis acid sites in solid-phase catalysts. Chiral metal-organic frameworks (MOFs) were synthesized by anchoring chiral hydroxylated molecules onto Zr-oxo clusters in achiral PCN-222(Cu). The resulting chiral MOFs exhibited regulated enantioselectivity of up to 83% ee in the asymmetric ring-opening of cyclohexene oxide. The chiral molecules created a multilevel microenvironment around the catalytic sites in the MOF, which played crucial roles and synergistically promoted chiral catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Yuanyuan Zhang, Yaoyu Liang, Xiaodan Zhao
Summary: The enantioselective electrophilic three-component thioarylation of alkenes using chiral selenide catalysis with free phenols as arylating sources has been disclosed. Various chiral phenols were obtained in high regio-, enantio-, and diastereoselectivities. Mechanistic studies showed that the transformation proceeded through carbon nucleophilic attack to give the products rather than the intramolecular rearrangement of phenolic ether intermediates.
Article
Chemistry, Multidisciplinary
Xuehao Li, Wenwen Cui, Qirong Deng, Xiuyan Song, Jian Lv, Daoshan Yang
Summary: An efficient and environmentally friendly method for synthesizing S-alkyl dithiocarbamates using visible light has been developed. The reaction has a broad substrate scope and good functional group tolerance in water. Importantly, no external photocatalyst is needed, making this method highly promising for applications in pharmaceutical and sulfur chemistry.
Article
Chemistry, Organic
Man Wang, Ming Li, Long Zhang, Ran Song, Daoshan Yang, Jian Lv
Summary: Photoredox catalysis involving Ir-III in combination with DABCO as a dual hydrogen-bonding donor and organic base can enable the direct gamma-C(sp(3))-H activation of saturated alpha-keto esters, leading to the synthesis of various 4-indolyl substituted 2-hydroxy-3-enoic acid esters. This method offers high yields and high enantioselectivity.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Wenwen Cui, Yu Li, Xufeng Li, Junxin Li, Xiuyan Song, Jian Lv, Yuan-Ye Jiang, Daoshan Yang
Summary: Transition-metal-catalyzed decarboxylative and C-H functionalization strategies have been extensively studied for the construction of Csp(2)-Csp(2), Csp(2)-Csp(3), and Csp(2)-Csp(3) bonds. However, research on the synthesis of Csp(3)-Csp(3) bonds using this strategy is surprisingly scarce. In this study, an efficient approach for the rapid formation of Csp(3)-Csp(3) bonds through copper-catalyzed decarboxylative Csp(3)-H functionalization is presented. This method offers a promising synthesis method for Csp(3)-Csp(3) bond construction in the field of synthetic and pharmaceutical chemistry.
CHINESE CHEMICAL LETTERS
(2023)
Review
Chemistry, Multidisciplinary
Daoshan Yang, Qiuli Yan, Enjie Zhu, Jian Lv, Wei-Min He
Summary: This review focuses on recent advances in C-S bond formation via visible-light photoredox catalysis, highlighting its potential in pharmaceutical synthesis, synthetic methodology development, and the application of sulfur-containing drugs.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Organic
Depeng Duan, Huixin Qiu, Mengdie Tang, Ran Song, Wen Si, Daoshan Yang, Jian Lv
Summary: This study reports a [4+2] cycloaddition catalyzed by Lewis acid HfCl4, leading to high yields of polysubstituted 4H-pyrans. The reaction conditions are mild and exhibit excellent selectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Huixin Qiu, Lirong Wen, Jian Lv
Summary: Visible-light-promoted [2+1] and [2+2] cycloaddition reactions of diazocarbonyls with olefins have been developed, and the regioselectivity and reactivity could be controlled by the addition of Rh-2(OAc)(4) in the presence of Ir(ppy)(3) catalyst.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Wenxuan Zhang, Jiaying Sun, Zhendong Lian, Ran Song, Daoshan Yang, Jian Lv
Summary: Here, we report a chiral catalyst-catalyzed asymmetric reaction between 2-alkynyphenols and aromatic ethers. The reaction shows high yield and excellent enantioselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Wenwen Cui, Xufeng Li, Guoju Guo, Xiuyan Song, Jian Lv, Daoshan Yang
Summary: In this study, a copper-catalyzed blue-light-induced free radical ring-opening reaction of sulfonium salts with dichalcogenides was developed. The method utilizes an inexpensive copper catalyst and has a broad substrate scope, allowing for the high-yield synthesis of alkyl chalcogenides. This reaction presents a novel ring-opening model for sulfonium salts, breaking the limitation of only nucleophilic ring-opening reactions to form C-heteroatom and C-C bonds.
Article
Chemistry, Applied
Ran Song, Caiqi Zhuo, Wen Si, Xiaoying Wu, Tianyi Guan, Daoshan Yang, Jian Lv
Summary: A metal-free method for synthesizing diarylmethylamines was developed using a 1,6-addition reaction of 1-aminobenzotriazole with p-quinone methides catalyzed by triphenylcarbenium tetrafluoroborate. The diarylmethylamines were obtained in moderate to good yields (up to 84%) under mild conditions, and showed unchanged activity after 6 reuses.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Xiaolong Zhu, Xiuyan Song, Xuan Li, Fengxiao Wang, Jian Lv, Min Jiang, Daoshan Yang
Summary: In this manuscript, a radical type ring-opening of sulfonium salts with heteroarenes under visible light conditions is reported. This method does not rely on noble metal photocatalysts or stoichiometric amounts of external oxidants, making it promising for the synthesis of organosulfur compounds and bioactive molecules. The developed photocatalytic system could inspire further applications of sulfonium salts in C(sp(3))-C(sp(2)) bond forming reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Jiaying Sun, Wenxuan Zhang, Ran Song, Daoshan Yang, Jian Lv
Summary: Catalytic direct [4 + 2] cycloaddition reactions and Friedel-Crafts reactions of ortho-alkynylnaphthols with benzofurans have been developed. They afford high yields of functionalized hydrobenzofuro[3,2-b]chromans and hydroarylation products, respectively, with high chemoselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xuan Li, Min Jiang, Junze Zuo, Xiuyan Song, Jian Lv, Daoshan Yang
Summary: This study reports a novel and efficient copper-catalyzed Sonogashira reaction between sulfonium salts and alkynes, promoted by visible light, for the synthesis of internal alkynes. The coexistence of nitrogen and phosphorus ligands in the system is crucial for the success of this reaction.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Organic
Ran Song, Zhendong Lian, Wei Feng, Tianyi Guan, Wen Si, Daoshan Yang, Jian Lv
Summary: A novel palladium-catalyzed decarboxylative O-allylation of phenols was developed. A gamma-methylidene-delta-valerolactone (GMDV) was identified as an efficient and selective allylation reagent, leading to the synthesis of allyl phenyl ethers in high yields under mild conditions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Man Wang, Rui Wang, Long Zhang, Wen Si, Ran Song, Daoshan Yang, Jian Lv
Summary: An efficient solvent-free radical oxyamination reaction has been demonstrated for the modification of carbonyl compounds adjacent to different chalcogens (e.g., S, O, and Se). This method does not require the use of a transition metal catalyst, chemical oxidant, or photocatalyst, and exhibits a wide substrate scope and high functional group tolerance.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Qiuli Yan, Wenwen Cui, Junxin Li, Guiyun Xu, Xiuyan Song, Jian Lv, Daoshan Yang
Summary: A highly efficient visible-light promoted benzylation method using riboflavin as a green photocatalyst has been developed for synthesizing C3-benzylated quinoxalin-2(1H)-one derivatives. This method offers a new approach for the synthesis of these derivatives, with potential applications in pharmaceutical and synthetic chemistry.
ORGANIC CHEMISTRY FRONTIERS
(2022)