Article
Biochemistry & Molecular Biology
Sodeeq Aderotimi Salami, Vincent J. Smith, Rui Werner Macedo Krause
Summary: Spirocyclic compounds, which are found in many active compounds, can be synthesized efficiently and yield high results through the Michael condensation of 3-dicyanomethylene-2H-indol-2-ones with isothiocyanate derivatives under aqueous and mechanochemical conditions. This novel protocol offers advantages such as solvent-free reactions, ambient temperature, short reaction times, experimental simplicity, and excellent yields, making it a suitable alternative to volatile organic solvents.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Organic
Motohiro Yasui, Haruna Ohbu, Maho Ishikawa, Tatsuhito Yoshida, Norihiko Takeda, Seiya Hirao, Takumi Abe, Masafumi Ueda
Summary: Spiro[indole-3,3'-pyrrolidine]-2'-ones were synthesized via one-pot chloroformylation-dearomatizing spirocyclization of tryptamine derivatives. Additionally, the thio equivalent spiro[indole-3,3'-pyrrolidine]-2'-thiones, which were previously unreported, were synthesized. The procedures are easily implemented, have a broad scope, and are transition-metal-free and cheap. To demonstrate the utility of the synthetic methodology, the spiro[indole-3,3'-pyrrolidine]-2'-ones were converted into heterocyclic scaffolds, such as an optically active spiroindoline and spirooxindole.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Wan Tang, Duan-Yang Yan, Kai-Cheng Liang, Ma Su, Feng Liu
Summary: We report a mild protocol for the synthesis of diverse indoline-fused heterocycles via a photoredox catalysis reaction. The reaction proceeds through a cascade of radical processes and exhibits wide functional-group compatibility.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Thomas Varlet, Damien Bouchet, Elsa Van Elslande, Geraldine Masson
Summary: A convenient and scalable dearomative hydroacylation reaction of indoles is reported. Using readily available aldehydes as acyl sources and TBADT as an inexpensive direct HAT photocatalyst, various indole derivatives are converted into synthetically interesting 2-acylindolines with good yields and diastereoselectivity under mild conditions. An asymmetric version of the reaction is successfully developed, and an experimental mechanistic investigation provides further insights into the assumed reaction pathway.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Liu Haoyang, Sun Shuangshuang, Ma Xianli, Chen Yanyan, Xu Yanli
Summary: A photosensitizer-free visible-light-promoted isocyanide insertion protocol has been developed for the synthesis of selenylated spiro[indole-3,3'-quinoline] derivatives. The method has the advantages of functional group tolerance, broad substrate scope, simple operation, and good yield. Several synthesized compounds showed potent cancer-cell-growth inhibitory activities.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Qian Wan, Jia-Hao Xie, Chao Zheng, Yao-Feng Yuan, Shu-Li You
Summary: In this study, a catalytic asymmetric dearomatization reaction of electron-deficient heteroarenes with alpha-substituted isocyanoacetates was reported, leading to a range of optically active pyrrolo[3,4-b]indole derivatives. The reaction yielded good results with high stereoselectivities, using a catalytic system consisting of a cinchona-derived amino-phosphine and silver oxide. This method features wide substrate scope, mild conditions, and provides a new strategy for developing asymmetric dearomatization reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Dharmendra Kumar, Dhananjay Chaudhary, Km Ishu, Suman Yadav, Naveen Kumar Maurya, Ruchir Kant, Malleswara Rao Kuram
Summary: A domino reaction sequence has been developed for the synthesis of pyrroloindolines, in which tryptamine derivatives and donor-acceptor diazo compounds are used as substrates. This reaction simultaneously forms three consecutive stereogenic centers, providing a convenient and efficient strategy for the construction of complex molecules. Copper catalysis enables the reaction to proceed smoothly at room temperature, and a wide range of substrates can be employed.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Shao-Cong Zhan, Ren-Jie Fang, Jing Sun, Chao-Guo Yan
Summary: Functionalized spiro[carbazole-3,5 '-pyrimidines] and spiro[carbazole-3,1 '-cyclohexanes] were efficiently synthesized in satisfactory yields with high diastereoselectivity using CuSO4-catalyzed multicomponent reactions. The initial compounds were further converted to new compounds using different oxidation methods.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Jiang Zhu, Jiaji Li, Lianjie Zhang, Shitao Sun, Lu Yang, Jiayue Fu, Hanyang Sun, Maosheng Cheng, Bin Lin, Yongxiang Liu
Summary: Spiro[indoline-3,3′-pyrrolidine] and spiro[indoline-3,3′-piperidine] derivatives were synthesized in a substitution-controlled manner using cationic gold(I) catalyst and Hantzsch ester (HEH). The optimal reaction conditions were determined by screening, and the functional group tolerances of these pathways were examined using synthetic substrates. Density functional theory calculations elucidated the endo and exo selectivities of these cyclizations, and a plausible mechanism for these transformations was proposed.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Dongyang Sun, Heng Zhang, Jigang Gao, Xukai Guan, Xiangshuo Qin, Guofeng Jiang, Guangliang Zhang, Liangyu Zheng, Suoqin Zhang
Summary: An efficacious method utilizing BINOL-type chiral imidodiphosphoric acid as catalyst was developed for the asymmetric [5 + 1] annulation reaction between 2-pyrrolylphenol and 1-methylindoline-2,3-dione, leading to a range of enantioenriched spiro[3,2'-morpholine-oxindole] derivatives incorporating a tertiary stereocenter with moderate to excellent yields and enantioselectivities under mild conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Organic
Divyang M. Patel, Paras J. Patel, Hitendra M. Patel
Summary: This Review discusses pioneering advances in catalytic stereoselective multicomponent reactions for the preparation of spiro derivatives, highlighting the stereoselective reactions and catalytic mechanisms used in different reactions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Xiao-Tong Lin, Cheng Zhao, Da-Ru Wang, Guang-Cheng Wu, Guo-Shu Chen, Shu-Jie Chen, Hai Ren, Dong-Sheng Deng, Yi-Bing Xu, Xiao-Wei Hu, Yun-Lin Liu
Summary: This study presented a BiCl3-mediated tandem cyclization reaction of tryptamine-ynamides, leading to the formation of pentacyclic spiroindoline scaffolds in moderate to excellent yields. The reaction also demonstrated the divergent synthesis of tricyclic indole derivatives with moderate yields by manipulating substrate structures, showcasing the synthetic utility of the methodology.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Review
Chemistry, Organic
Fangzhi Hu, Yao-Bin Shen, Liang Wang, Shuai-Shuai Li
Summary: This review provides a timely account of the emerging hydride transfer-involved dearomatization reaction in organic synthesis. It categorizes the reaction based on different hydride acceptors, vinylogous imines and quinone methides, which initiate the cascade hydride transfer/dearomative cyclization process to dearomatize indoles and phenols. The limitations, challenges, and future directions in this field are also discussed.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Miyuki Yamaguchi, Ryoya Hagiwara, Hana Muto, Kanami Gayama, Hideyuki Konishi, Kei Manabe
Summary: A palladium-dihydroxyterphenylphosphine catalyst was used for the selective C3-arylation of tryptamine derivatives with aryl nonaflates, leading to the formation of C3a-arylated pyrroloindolines via intramolecular cyclization. Complex formation between the lithium salts of DHTP and the tryptamine derivative is proposed as the key factor for promoting arylation at the C3-position of the indole ring. Additionally, C4a-arylated pyridoindolines were obtained by reactions using homotryptamine derivatives.
Article
Chemistry, Multidisciplinary
Kosuke Okada, Ken-ichi Ojima, Hirofumi Ueda, Hidetoshi Tokuyama
Summary: The synthesis of (+)-pleiocarpamine, (+)-voacalgine A and (+)-bipleiophylline was achieved in this study. The 10-step synthesis of (+)-pleiocarpamine features the construction of stereochemistry at the C16 position by radical cyclization and the synthesis of the highly strained cage-like structure via Pd-catalyzed intramolecular aromatic C-H functionalization. By modifying the biomimetic aerobic oxidative coupling of tryptophane derivatives catalyzed by FePc(CO2H)(8), the oxidative coupling of (+)-pleiocarpamine with pyrocatechuic acid produced (+)-voacalgine A. The total synthesis of (+)-bipleiophylline was completed by the second coupling of (+)-voacalgine A with (+)-pleiocarpamine or the one-pot couplings of 2 equiv of (+)-pleiocarpamine with pyrocatechuic acid.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Xin-Wei Wang, Wen-Jun Huang, Han Wang, Bo Wu, Yong-Gui Zhou
Summary: In this study, a catalytic asymmetric Pictet-Spengler reaction on the benzene ring of indoles was achieved using chiral phosphoric acid, resulting in the synthesis of polycyclic indole derivatives with Spiro quaternary stereocenters in excellent yields and enantioselectivities. The reaction could be conducted on a gram scale without any loss of activity or enantioselectivity.
Article
Chemistry, Applied
Yuan He, Zilong Huang, Juan Ma, Jie Lin, Yong-Gui Zhou, Zhengkun Yu
Summary: A transition-metal-free method was developed for the cleavage of C-H bonds in olefins. By using vinylsulfonium salts and sodium azide, sulfanyl-azidoalkene compounds were synthesized and further transformed into various derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Yi-Xuan Ding, Zhou-Hao Zhu, Mu-Wang Chen, Chang-Bin Yu, Yong-Gui Zhou
Summary: In this study, the asymmetric hydrogenation of all-carbon aromatic rings was achieved using rhodium/diphosphine catalysts. The introduction of chiral diphosphine ligands with steric hindrance and strong electron-donating properties was key to the success in obtaining axially chiral cyclic compounds with high enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Xiao-Qing Wang, Bo Wu, Yu-Qing Bai, Xiao-Yong Zhai, Yong-Gui Zhou
Summary: This study presents an easy-to-operate and efficient CuH-catalyzed consecutive asym-metric hydrosilylation/dehydrocoupling polymerization method for synthesizing chiral poly(silyl ether)s. The method offers advantages such as atom economy, broad substrate scope, and high stereoselectivity.
EUROPEAN POLYMER JOURNAL
(2022)
Article
Chemistry, Organic
Kun Wang, Yan-Jiang Yu, Xiao-Qing Wang, Yu-Qing Bai, Mu-Wang Chen, Yong-Gui Zhou
Summary: In this study, a palladium-catalyzed asymmetric hydrogenation of unprotected 3-substituted indoles was developed, providing a series of 3-substituted indolines in high yields with good enantioselectivity (<= 94.4:5.6 er). The bulky bisphosphine ligand played a crucial role in controlling the enantioselectivity. In addition, gram-scale hydrogenation experiments and product derivatizations were successfully conducted.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
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, Organic
Jie Lin, Zilong Huang, Juan Ma, Bao-Hua Xu, Yong-Gui Zhou, Zhengkun Yu
Summary: Efficient palladium-catalyzed reactions were utilized to synthesize diverse compounds, including trisubstituted 1,3-dienes and tetrasubstituted allenes. The chemo- and regioselectivities were controlled to obtain structurally diverse products.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yunlong Li, Wenchao Jiang, Jie Lin, Juan Ma, Bao-Hua Xu, Yong-Gui Zhou, Zhengkun Yu
Summary: In this study, triple C-H bond activation of aryl enaminones was achieved to access naphtho[1,8-bc]pyrans through oxidative annulation. Depending on the steric and/or electronic environment around the aryl moiety of the enaminones or the electronic impact from the alkynes, 1-naphthols might be formed as the sole products. By using propargyl alcohols as masked terminal alkynes, functionalized but-2-ene-1,4-diones were obtained through rhodium(III)- or rhodium(I)-catalyzed internal alkenyl C-H bond activation. The resulting naphtho[1,8-bc]pyrans exhibited high fluorescence and could be further transformed by chlorination, bromination, and difluoromethylation, demonstrating the potential applicability of the synthetic protocol.
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, 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)
