Article
Chemistry, Organic
Cheng-Yu Chen, Jing-Hao Zhao, Li-Xue Xiong, Feiyi Wang, Guichun Yang, Chao Ma
Summary: A selective arylation of donor-acceptor diazo compounds with aniline derivatives catalyzed by Lewis acidic boranes is developed, providing an efficient method for the synthesis of diarylacetates under metal-free conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yu-Han Lu, Si-Yu Mu, Hong-Xia Li, Jun Jiang, Chao Wu, Min-Hang Zhou, Wen-Tao Ouyang, Wei-Min He
Summary: By utilizing formaldehyde as an atom-economical carbonyl synthon, a novel EtOH-catalyzed electrochemical multicomponent synthesis of imidazolidine-fused sulfamidates was developed. The reaction provided a wide range of products in good to excellent yields under organic oxidant-free, energy-saving, and mild conditions. Mechanistic studies revealed that the in situ generated ethoxide played a crucial role in producing aminomethylene radicals at a lower voltage.
Article
Chemistry, Organic
Jun Shi, Rui-An Wang, Wei Wu, Jun-Rong Song, Qin Chi, Wei-Dong Pan, Hai Ren
Summary: This study reports a safe and convenient copper-catalyzed selective oxidation method using atmospheric oxygen as the oxidant. The method allows for the oxidative rearrangement of indole compounds, leading to the formation of various functionalized products. This represents a significant advance in the field of indole oxidation.
Article
Chemistry, Organic
Linjuan Jiang, Hui Hu, Yuanhong Liu
Summary: A copper-catalyzed regioselective C-2 alkenylation of quinoline N-oxides with alkynes and pinacol diborane has been developed, providing efficient access to a wide variety of deoxygenated 2-alkenyl quinolines with good functional group tolerance, especially with unsymmetrical alkynes such as aryl(alkyl)acetylenes and enynes.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Gong Chen, Kenta Arai, Kazuhiro Morisaki, Takeo Kawabata, Yoshihiro Ueda
Summary: A method for selective C(sp(3))-H amidation of N,N-dimethylanilines was developed, exclusively targeting the N-methyl group for amidation while leaving the C(sp(2))H bonds on the aromatic ring untouched.
Article
Chemistry, Multidisciplinary
Nikolaos Kaplaneris, Marcelo Vilches-Herrera, Jun Wu, Lutz Ackermann
Summary: Catalyzed C-H activation is an important tool for molecular assembly, enabling efficient assembly of complex structures. Ruthenium catalysis offers cost-effective and mild C-H functionalization with unique reactivity, contributing to sustainability in industrial settings. Sustainable ruthenium-catalyzed C-H activation can be achieved using water as a reaction medium.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
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
Xu Wang, Yuting Xue, Weinan Hu, Linlin Shi, Xinju Zhu, Xin-Qi Hao, Mao-Ping Song
Summary: A copper-catalyzed delta-regioselective C(sp(3))-H heteroarylation of N-fluorosulfonamides has been developed, providing a practical strategy for the functionalization of heteroarenes and amides via forging a C(sp(3))-C(sp(2)) bond. A broad range of heteroarenes were well tolerated and reacted with various N-fluorosulfonamides to give the corresponding heteroarylated amides in good yields. Notably, all types of delta-C(sp(3))-H bonds in the N-fluorosulfonamides could be regioselectively activated through the 1,5-HAT process.
Article
Chemistry, Physical
Kathiravan Murugesan, Arunachalam Sagadevan, Lu Peng, Oleksandr Savateev, Magnus Rueping
Summary: In this study, a simple and scalable method for synthesizing aldehydes, ketones, and amides from abundant raw materials was developed. The method utilizes a photoactive catalyst and molecular oxygen, and has potential applications in drug development and understanding biological pathways.
Article
Chemistry, Multidisciplinary
Zhi-Jiang Jiang, Si-Han Xu, Yuhang Su, Erxun Hu, Jiawei Han, Jian-Fei Bai, Bencan Tang, Jia Chen, Zhanghua Gao
Summary: A nickel-catalyzed hydrogen isotope exchange has been developed using acetone-d6 as the deuterium source. With the assistance of 2-pyridones, the reaction exhibits improved kinetic features of H/D exchange, leading to the efficient synthesis of regioselective labeled aryl and alkyl carboxamides.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Ozgur Yilmaz, Cagatay Dengiz, Marion H. Emmert
Summary: This study details the development of a mild protocol for the alpha-C-H cyanation of tertiary amines and its successful application in late-stage functionalization. The method is not only applicable to a variety of substrates, but also tolerates numerous functional groups, demonstrating a broad substrate scope and high practicality.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Jianming Liu, Xiaopei Wang, Zhiyue Wang, Yan Yang, Qinghu Tang, Hongchi Liu, Hanmin Huang
Summary: A copper-catalyzed, aerobic oxidative C-H/C-H cyclization reaction was developed for the cleavage of C-H and N-H bonds in 3-phenylindoles. The reaction showed good tolerance to a variety of 3-phenylindoles and provided high yields of indole-containing polycyclic aromatic hydrocarbons (PAH). The isolation of di- and tri-indole intermediates allowed for an evaluation of the reaction mechanism, highlighting the role of the substrate as a catalyst. Mechanistic studies revealed that the substrate accelerates the reaction by transforming the less active di-indole intermediate into a tri-indole intermediate.
Article
Chemistry, Multidisciplinary
Hui Yang, Zi-Qi Yang, Su-Zhen Zhang, Wen-Wen Zhang, Qing Gu, Shu-Li You
Summary: Chiral dihydrobenzofuran is a valuable synthetic fragment in both medicinal and organic chemistry. Efficient rhodium(III)-catalyzed chemoselective and enantioselective C-H functionalization/[3+2] annulation of N-phenoxyacetamides with 1,3-dienes is reported. In the presence of 5 mol% CpRh complex, various chiral dihydrobenzofurans were synthesized in up to 79% yield and 98% ee. This reaction proceeds under mild conditions with excellent functional group compatibility.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Organic
Kuppan Ramachandran, Pazhamalai Anbarasan
Summary: An efficient rhodium-catalyzed method for the synthesis of C2-alkylated NH-free indoles has been achieved. This method offers several advantages, including the use of traceless directing group, good functional group tolerance, and broad applicability.
Article
Chemistry, Organic
Bholanath Garai, Molla Rahamat Ali, Rajib Mandal, Basker Sundararaju
Summary: This study demonstrates the C(8)-selective nucleophilic cascade cyclization of quinoline N-oxide with easily derived 1,6-enyne from phenol derivatives. Various quinoline N-oxide and alkynes are found to be suitable for producing a library of quinoline N-oxide tethered cis-hydrobenzofurans with high yields and excellent functional group tolerance. The utility of the protocol has been achieved through post-synthetic modification of the cyclized product. Mechanistic studies reveal a base-assisted internal electrophilic-type substitution (BIES)-type pathway for C-H bond activation, and electrospray ionization mass spectrometry (ESI-MS) analysis confirms the formation of a key five-membered cobaltacycle.
Article
Biochemistry & Molecular Biology
Haoxuan Yuan, Yinfeng Guo, Zhijing Zhang, Hongkai Sha, Yicheng He, Xinfang Xu, Wenhao Hu
Summary: A Rh-2(OAc)(4) catalyzed three-component reaction enables the direct assembly of succinimide and isatin hybrid molecules with good-to-high yields and excellent stereoselectivity. The synthesized products exhibit significant anticancer potency, especially compounds 4g and 4r.
MOLECULAR DIVERSITY
(2023)
Article
Biochemistry & Molecular Biology
Jingjing Huang, Yufei Chen, Yinfeng Guo, Ming Bao, Kemiao Hong, Yuanqing Zhang, Wenhao Hu, Jinping Lei, Yongqiang Liu, Xinfang Xu
Summary: A series of hybrid compounds were synthesized and their antiproliferative activity against tumor cells was evaluated. Promising compounds were found to selectively inhibit specific cell lines, suggesting potential molecular mechanisms.
MOLECULAR DIVERSITY
(2023)
Article
Biochemistry & Molecular Biology
Mengting Liu, Xiongda Xie, Ming Bao, Zhijing Zhang, Wenhao Hu, Yu Qian, Xinfang Xu
Summary: A gold-catalyzed carbocyclization/imidization cascade reaction has been developed for the synthesis of functionalized nitrones. The resulting products can be further converted into substituted naphthalenol analogues and exhibit potential tumor suppression activity.
MOLECULAR DIVERSITY
(2023)
Article
Chemistry, Multidisciplinary
Ming Bao, Xiongda Xie, Jingjing Huang, Michael P. Doyle, Zhi Ren, Haibo Yue, Xinfang Xu
Summary: In this study, an Ag/Au-catalyzed cascade reaction of alkyne embedded diazoketones with indoles has been reported. Mechanistic studies indicate that the reaction involves a [4+2] cycloaddition followed by a retro-Michael addition/carbene N-H insertion process with gold catalysis, and a dearomatization/rearomatization sequence with silver catalysis, leading to the selective construction of N-doped polycyclic aromatic hydrocarbons (PAHs) with diverse structures and functional groups.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Weichen Xiong, Su Zhou, Xinke Zhang, Jingyu Zhao, Jingjing Huang, Wenhao Hu, Xinfang Xu
Summary: A gold-catalyzed oxidative three-component reaction of terminal alkynes with alcohols and quinone monoimines has been developed for the synthesis of alpha-ketoacetals. This one-pot process involves an oxidation-oxyalkylation-aryloxylation sequence, enabling the functionalization of terminal alkynes and introducing three oxygen atoms on the C-C triple bond.
Article
Chemistry, Physical
Ming Bao, Karlos Lopez, Raj Gurung, Hadi Arman, Michael P. Doyle
Summary: A highly enantioselective synthesis of chiral dihydro-3H-carbazole-2-carboxylate derivatives is achieved via a one-pot cascade reaction catalyzed by nickel(II) perchlorate hexahydrate and scandium(III) trifluoromethanesulfonate. The reaction proceeds under mild conditions and provides the desired products in high yields and enantioretention. Furthermore, these dihydro-3H-carbazole-2-carboxylates can be transformed into decarboxylated compounds through hydrolysis and decarboxylation under unexpectedly mild reaction conditions, giving moderate yields with high retention of enantiomeric purity.
Article
Chemistry, Physical
Kemiao Hong, Jirong Shu, Shanliang Dong, Zhijing Zhang, Yicheng He, Mengting Liu, Jingjing Huang, Wenhao Hu, Xinfang Xu
Summary: An achiral dirhodium complex and chiral phosphoric acid cooperatively catalyze the asymmetric three-component reaction of enynal with alcohol and imine, resulting in the formation of chiral alpha-furyl-beta-amino carboxylates with good to high yields and excellent stereoselectivity. This method efficiently prepares complex furan derivatives with adjacent quaternary and tertiary stereocenters.
Article
Chemistry, Multidisciplinary
Luca De Angelis, Graham C. Haug, Gildardo Rivera, Soumen Biswas, Ammar Al-Sayyed, Hadi Arman, Oleg Larionov, Michael P. Doyle
Summary: One important reaction of 1,2,3-triazines is the inverse electron demand Diels-Alder (IEDDA) cycloaddition with a dienophile, which proceeds through nucleophilic addition to the triazine followed by N-2 loss and cyclization. Previous studies have not provided a comprehensive understanding of the site of nucleophilic addition on the triazine. This study investigated the C-, N-, H-, O-, and S-nucleophilic additions on 1,2,3-triazine and 1,2,3-triazine-1-oxide frameworks and revealed the differentiation of addition at the 4- and 6-positions. Computational studies further examined the factors influencing the outcomes of these reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Soumen Biswas, Luca De Angelis, Gildardo Rivera, Hadi Arman, Michael P. Doyle
Summary: 1,2,3-Triazine 1-oxides are highly effective substrates for inverse electron demand Diels-Alder reactions. These stable heterocyclic compounds, formed from vinyldiazoacetates via reaction with tert-butyl nitrite, undergo clean nucleophilic addition reactions with amidines to form pyrimidines, with beta-ketocarbonyl compounds and related nitrile derivatives to form polysubstituted pyridines, and with 3/5-aminopyrazoles to form pyrazolo[1,5-a]pyrimidines, in high yields. These reactions, catalyzed by bases, are rapid at room temperature and allow for a range of structural modifications.
Article
Chemistry, Organic
Michael P. Doyle, Ming Bao
Summary: This study achieved a highly enantioselective synthesis of substituted pyrrolidines and 1,2-oxazinanes via stereoretentive [3 + 2]/[3 + 3]-cycloaddition of nonracemic donor-acceptor cyclopropanes with imines, triazines, and nitrones. The reactions were conducted under mild conditions and showed good to high yields with broad applicability. Compared to previous approaches using racemic cyclopropane reactants and chiral ligand catalysts, this study utilized enantioenriched donor-acceptor cyclopropanes as reactants with achiral catalysts.
Article
Multidisciplinary Sciences
Luca De Angelis, Chao Pei, Ana L. Narro, Daniel Wherritt, Rene M. Koenigs, Michael P. Doyle
Summary: The synthesis and characterization of organic compounds with unique atom or functional group connectivity is a significant interest for chemists. Polycarbonyl compounds, in which multiple carbonyl groups are directly adjacent and influence each other's reactivity, have been extensively studied. However, little is known about 1,2,3,4-tetracarbonyl compounds. In this study, a synthesis strategy involving C-nitrosation of enoldiazoacetates is reported, which allows for the synthesis of 1,2,3,4-tetracarbonyl compounds where each carbonyl group is orthogonally masked.
NATURE COMMUNICATIONS
(2023)
Review
Chemistry, Physical
Ming Bao, Michael P. Doyle
Summary: The [3+n]-cycloaddition reactions using chiral catalysts and racemic cyclopropanes or achiral catalysts and chiral, non-racemic cyclopropanes have proven to be important transformations for the synthesis of carbocyclic and heterocyclic compounds, showing both mechanistic and structural advantages in ring formation.
Article
Chemistry, Multidisciplinary
Yang Zheng, Jingxing Jiang, Yue Li, Yongliang Wei, Junqi Zhang, Jundie Hu, Zhuofeng Ke, Xinfang Xu, Liming Zhang
Summary: An oxidative strategy is reported for the direct access of alpha-oxo BMIDA gold carbenes from BMIDA-terminated alkynes. These BMIDA gold carbene species can insert into various C-H bonds and undergo other reactions, leading to the formation of structurally diverse alpha-BMIDA ketones. The role of BMIDA is found to be an electron-donating group that reduces the electrophilicity of the gold carbene center, as supported by DFT studies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Ming Bao, Karlos Lopez, Raj Gurung, Hadi Arman, Michael P. Doyle
Summary: A highly enantioselective synthesis of chiral dihydro-3H-carbazole-2-carboxylate derivatives is achieved via a one-pot cyclopentannulation-rearrangement cascade reaction. The reaction is catalyzed by nickel(II) perchlorate hexahydrate and scandium(III) trifluoromethanesulfonate, and involves the use of 3-methylindole and non-racemic donor-acceptor cyclopropanes. The resulting products show high yields and enantioretention under mild reaction conditions, and further transformation into decarboxylated compounds can be achieved with moderate yields and high enantiomeric purity.
