Review
Chemistry, Physical
Mercedes Zurro, Aitor Maestro
Summary: This paper reviews the recent literature on the catalytic methodologies for the derivatization of aza-QM, including organocatalytic and organometallic approaches. The review analyzes various catalytic systems, involving chiral NHC carbenes, phosphoric acids, phosphoramidites, phosphine, copper, and palladium catalysis, showcasing their applicability for the synthesis of a diverse array of N-containing compounds, many of which exhibit biological activity.
Review
Chemistry, Organic
Yu-Hong Ma, Xiao-Yu He, Qing-Qing Yang, Amina Boucherif, Jun Xuan
Summary: This review summarizes recent advancements in organocatalytic asymmetric cycloaddition reactions involving ortho-quinone methides (o-QMs). Organocatalysts have become a privileged class of catalytic systems in asymmetric synthesis, leading to significant achievements worldwide. The review focuses on works published from January 2016 to December 2020, excluding discussions on catalytic systems combining metal catalysts and organocatalysts.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Hong Liu, Kai Li, Shengli Huang, Hailong Yan
Summary: This study reports the first isolation and comprehensive characterization of vinylidene orlho-quinone methides (VQMs), demonstrating their significant role in asymmetric catalysis and potential as starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(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, Applied
Artur Przydacz, Aleksandra Topolska, Anna Skrzynska, Sebastian Frankowski, Lukasz Albrecht
Summary: This manuscript presents the application of amino isobenzofulvene intermediates as pentaenamines in a 1,6-addition reaction. The alkylation of the indene ring in indene-2-carbaldehydes with para-quinone methides was achieved, with the stereoselectivity controlled by C-2-symmetric 2,5-diphenylpyrrolidine. The developed process utilizes the reactivity of amino isobenzofulvene intermediates derived from indene-2-carbaldehydes in a non-cycloadditive manner.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Deyuan Meng, Jing He, Woojin Yoon, Hoseop Yun, Jung Tae Han, Jaesook Yun
Summary: In this study, the catalytic 1,6-addition of chiral alkyl copper nucleophiles generated from borylalkenes and a copper-hydride catalyst was successfully conducted under mild conditions. The controlled chemo- and stereoselectivity played a crucial role in the reductive coupling process, resulting in efficient synthesis of asymmetric 1,6-adducts of p-quinone methides through multicomponent and catalytic tandem reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Kyeong Seop Kim, Dae Young Kim
Summary: In this study, chiral 2-amino-4H-chromene derivatives were synthesized from 2-alkyl-substituted phenol derivatives via a one-pot cascade reaction using a binaphthyl-modified organocatalyst with low catalyst loading (1.25 mol%). The reaction showed moderate to high yields and excellent enantioselectivities.
SYNTHETIC COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Wu Yuzhu, Shen Panpan, Duan Wenzeng, Ma Yudao
Summary: The first carbene-catalyzed enantioselective 1,6-conjugate addition of boron to para-quinone methides was achieved using a commercially available chiral triazolium and bis(pinacolato)diboron. This reaction features mild conditions, broad substrate scope, excellent functional group tolerance, and good yield and enantioselectivity. Remarkably, even in the absence of any transition metals, the reaction proceeded well with just 0.1 mol% of catalyst loading without significant loss of yield and enantioselectivity, although longer reaction time was required.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Xianghui Liu, Kai Wang, Yan Liu, Can Li
Summary: This work presents a water triggered chemo-divergent enantioselective spiro-annulation and cascade reaction catalyzed by a chiral organic base. By adjusting the ratio of water in the solvent, two new highly efficient asymmetric reactions were developed for the divergent synthesis of spiro- and fused-indanone scaffolds with excellent enantioselectivities. Mechanistic investigations suggest the importance of interfacial hydrogen bonding in achieving switchable reaction pathways.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Biochemistry & Molecular Biology
Dae Young Kim
Summary: A one-pot strategy has been developed for the synthesis of multisubstituted 3,4-dihydrocoumarins with high yields and excellent diastereoselectivity. This approach involves C-H oxidation and cyclization cascade reactions of 2-alkyl phenols and oxazolones in the presence of silver oxide and p-toluenesulfonic acid as catalysts.
Article
Chemistry, Multidisciplinary
Esteban Matador, Javier Iglesias-Siguenza, David Monge, Pedro Merino, Rosario Fernandez, Jose M. Lassaletta
Summary: A highly enantio- and diastereoselective thiourea-catalyzed dearomatization of isoquinolines has been developed using N-tert-butylhydrazones as key neutral reagents, leading to the formation of appealing dihydroisoquinoline derivatives with excellent stereocontrol. Experimental and computational data support the generation of highly ordered complexes that play a crucial role in the selective and high-yielding transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Guangmiao Wu, Tao Li, Fuhai Liu, Yulong Zhao, Shiqiang Ma, Shouchu Tang, Xingang Xie, Xuegong She
Summary: An efficient thiourea-catalyzed 1,6-conjugate addition of indoles to para-quinone methides (p-QMs) was developed, where p-QMs were activated by a weak hydrogen-bond effect. The reaction features mild conditions and a wide substrate scope, allowing for the synthesis of a series of C-3 bisaryl methine substituted indoles in high yield.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Organic
Xiao Lin, Boming Shen, Ziyang Wang, Yuyu Cheng, Xuling Chen, Pengfei Li, Peiyuan Yu, Wenjun Li
Summary: In this study, an asymmetric organocatalytic reaction was developed for the first time, enabling the remote 1,10-addition of alkynyl indole imine methides generated in situ from alpha-(6indolyl) propargylic alcohols with thiazolones. The reaction yielded axially chiral tetrasubstituted allenes featuring vicinal sulfur-containing quaternary carbon stereocenters, with high yields and excellent stereoselectivities. The scalability of the reaction and the chemical transformations of the 1,10-adduct were also investigated. Control experiments and DFT calculations were conducted to elucidate the reaction mechanism.
Article
Chemistry, Physical
Guosong Shen, Faqian He, Wansen Xie, Huanchao Gu, Xiaoyu Yang
Summary: Asymmetric diastereodivergent catalysis is an important strategy for accessing different stereoisomers of a molecule. In this study, a new method for the asymmetric diastereodivergent synthesis of chromanes with C2,C3-contiguous tetrasubstituted stereocenters was reported using chiral phosphoric acid catalysts.
Article
Chemistry, Applied
Zaneta A. Mala, Mikolaj J. Janicki, Robert W. Gora, Krzysztof A. Konieczny, Rafal Kowalczyk
Summary: Dithiomalonates have been shown to be active nucleophiles in stereoselective additions, with Cinchona squaramides facilitating chirality transfer and mechanochemical approach proving to be effective.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Polymer Science
Xiao-Qing Wang, Yu-Qing Bai, Kun Wang, Bo Wu, Yong-Gui Zhou
Summary: This paper presents a metal-free insertion polymerization method for constructing carbon-heteroatom bonds in the main chain. Sulfoxonium ylides are used as monomers to produce polythioethers and aromatic polyamines with high yield and molecular weight. The method features mild conditions, easy operation, and a wide range of substrate applicability.
EUROPEAN POLYMER JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Ying Zhou, Xin Yue, Feng Jiang, Jianwei Sun, Wengang Guo
Summary: This article reports an efficient organocatalytic formal N-H insertion reaction of arylamines with alpha-keto sulfoxonium ylides bearing two aryl groups, resulting in a broad range of alpha-tertiary aminoketones with good to excellent yields and enantioselectivities (up to 90% yield and 94% ee). The usefulness of this methodology is further demonstrated by the facile synthesis of enantioenriched 2-amino-1,2-diarylethanol bearing two different aryl groups, which represents an important building block with limited access.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Wengang Guo, Ying Zhou, Hongling Xie, Xin Yue, Feng Jiang, Hai Huang, Zhengyu Han, Jianwei Sun
Summary: In this study, the first metal-free asymmetric H-X bond insertion of its kind was achieved by utilizing visible light as a promoter and a chiral phosphoric acid as a catalyst. Under mild conditions, alpha-diazoesters and aryl amines smoothly underwent N-H bond insertion to form enantioenriched alpha-aminoesters with high efficiency and good enantioselectivity. The key to success was the use of DMSO as an additive, which facilitated the rapid capture of the highly reactive free carbene intermediate to form a domesticated sulfoxonium ylide.
Article
Chemistry, Multidisciplinary
Xiang Li, Gao-Wei Wang, Li-Xia Liu, Chang-Bin Yu, Yong-Gui Zhou
Summary: Here, the authors describe the first example of palladium-catalyzed asymmetric hydrogenolysis of easily accessible aryl triflates for the construction of axially chiral biaryl scaffolds. The resulting chiral biaryl compounds were used to prepare axially chiral monophosphine ligands, which were further employed in palladium-catalyzed asymmetric allylic alkylation with excellent enantioselectivities and high branched and linear ratios, highlighting the potential utility of this methodology.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Tong Niu, Li-Xia Liu, Bo Wu, Yong-Gui Zhou
Summary: A series of [2,2]paracyclophane-based tridentate PNO ligands with planar chirality were designed and synthesized. These easily prepared chiral tridentate PNO ligands were successfully applied to the iridium-catalyzed asymmetric hydrogenation of simple ketones, providing chiral alcohols with high efficiency and excellent enantioselectivities (up to 99% yield and >99% ee). Control experiments demonstrated the indispensability of both N-H and O-H in the ligands.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Zilong Huang, Jie Lin, Mingrui Li, Zhengkun Yu, Yong-Gui Zhou
Summary: A zinc(II)-catalyzed [2+2+1] annulation reaction of internal alkenes, diazooxindoles, and isocyanates was developed for the efficient synthesis of multisubstituted spirooxindoles. This multi-component transformation involves the in situ formation of a sulfur-containing spirocyclic intermediate, followed by a 1,3-dipolar addition reaction of the intermediate with the internal alkene, resulting in a formal [2+2+1] annulation in a one-pot manner. The synthetic protocol utilizes a low-toxicity main group metal catalyst, readily available reagents, and provides high yields of up to 96% for the synthesis of multisubstituted spirooxindole derivatives.
Review
Chemistry, Multidisciplinary
Xiao Xiao, Kaini Xu, Zhong-Hua Gao, Zhou-Hao Zhu, Changqing Ye, Baoguo Zhao, Sanzhong Luo, Song Ye, Yong-Gui Zhou, Senmiao Xu, Shou-Fei Zhu, Hongli Bao, Wei Sun, Xiaoming Wang, Kuiling Ding
Summary: Enzymes are essential for biological transformations and have attracted great attention for their structures and functions. Biomimetic chemistry has rapidly developed in response to the demand for bioactive molecules and efficient synthesis. Biomimetic asymmetric catalysis, inspired by enzymes, has been recognized as one of the most promising strategies for producing valuable chiral compounds. This review summarizes the evolution of biomimetic asymmetric catalysis in terms of biomimetic design, catalyst development, and catalytic transformations, providing insights into bridging the gap between bio-catalysis and chemical synthesis.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Organic
Zheng Liu, Sheng-Mei Lu, Bao-Qian Zhao, Hao-Dong Chen, Mu-Wang Chen, Yong-Gui Zhou
Summary: A method using zinc chloride was developed to purify compounds with pyridine structure from Mitsunobu reaction mixtures, and a sulfide anion was used to release bipyridines from Ullmann coupling reaction mixtures by competitively coordinating the copper ion. These improvements enabled the facile synthesis of the chiral 2,2'-bipyridine ligand (R-a,S,S)-C3-ACBP, achieving an overall yield of 48% at a 7 gram scale within 3-4 days without column chromatography.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Ying Zhou, Yan Zhang, Canghai Yu, Xin Yue, Feng Jiang, Wengang Guo
Summary: This study discovered a method that utilizes high energy intermediates to construct valuable chiral products. By catalytic asymmetric protonation of in situ generated ammonium ylide using chiral Bronsted acid under visible-light irradiation, the desired α-amino esters were obtained with moderate to high enantioselectivity and yield. This method not only demonstrates the compatibility of chiral phosphoric acid catalysis with free carbene insertion reactions, but also indicates the significance of arylamine's pKa value in tuning the enantioselectivity of the reaction.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Organic
Feng Jiang, Tengfei Meng, Ying Zhou, Zhenying Xiong, Yupei Zhao, Wengang Guo
Summary: We report an enantio- and diastereodivergent synthesis of enantioenriched fluorenes with broad substrate scope and high enantioselectivity (up to 99% ee) under low catalyst loading (0.1 mol %). The success of this method lies in the pseudo-diastereodivergent desymmetrization of stereoisomers of meso-epoxides enabled by the same organocatalyst. Furthermore, some of the chiral fluorenes obtained exhibit high fluorescence quantum yields (up to 76.6%), as evidenced by photophysical properties studies.
Article
Chemistry, Multidisciplinary
Xin Yue, Ying Zhou, Yan Zhang, Tengfei Meng, Yupei Zhao, Wengang Guo
Summary: In this study, we have developed a sequential visible-light-promoted Wolff rearrangement of 1-diazonaphthalen-2(1H)-ones, followed by capturing the in situ generated ketene intermediates with various alcohols, resulting in diverse 1H-indene-3-carboxylates in moderate to good yields under mild reaction conditions. The broad substrate scope, high functional group tolerance, and robust conditions make the resulting derivative a versatile platform for the synthesis of numerous bioactive molecules.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Li-Xia Liu, Yu-Qing Bai, Xiang Li, Chang-Bin Yu, Yong-Gui Zhou
Summary: Combining base-promoted retro-sulfa-Michael addition with palladium-catalyzed asymmetric allenylic alkylation, a streamlined synthesis of chiral thiochromanones containing two central chiralities (including a quaternary stereogenic center) and an axial chirality (allene unit) was successfully achieved, with yields up to 98%, dr of 49.0:1, and >99% ee.
Article
Chemistry, Organic
Wen-Jun Huang, Li-Xia Liu, Yong-Gui Zhou, Bo Wu, Guo-Fang Jiang
Summary: We report a Bronsted acid-catalyzed C6 functionalization of 2,3-disubstituted indoles with 2,2-diarylacetonitriles for efficient construction of cyano-substituted all-carbon quaternary centers with excellent yields. The synthetic utility was demonstrated by the conversion of the cyano-group which enables the divergent preparation of aldehydes, primary amines and amides. Control experiments suggested that this process involves C-H oxidation of 2,2-diarylacetonitriles to in situ generate d,d-disubstituted p-quinone methide intermediates. This protocol provides an efficient method for C6 functionalization of 2,3-disubstituted indoles to construct all-carbon quaternary centers.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zhibing Weng, Ying Zhou, Xin Yue, Feng Jiang, Wengang Guo
Summary: In this study, catalytic asymmetric alpha-regioselective Michael additions of vinylogous alpha-ketoester enolates were conducted efficiently using a chiral bifunctional organocatalyst. The reactions yielded Rauhut-Currier type products with high yields and excellent regio- and enantioselectivities.
Article
Chemistry, Multidisciplinary
Wengang Guo, Feng Jiang, Shijia Li, Jianwei Sun
Summary: A catalytic asymmetric azidation reaction for the efficient synthesis of alpha-azido ketones bearing a labile tertiary stereocenter is disclosed. Detailed mechanistic studies provided important insights into the reaction pathway, and a simplified alternative protocol using a cheaper HN3 source was developed.
