Review
Chemistry, Applied
Daniel Gavina, Marcos Escolano, Javier Torres, Gloria Alzuet-Pina, Maria Sanchez-Rosello, Carlos del Pozo
Summary: Substituted and annulated pyrroles containing chiral centers can be accessed through organocatalytic enantioselective Friedel-Crafts alkylation (FCA) reaction. These compounds are interesting due to their natural occurrence and diverse biological activities. In the past two decades, significant synthetic efforts have been made to develop asymmetric transformations involving pyrroles in the FCA reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Xuesuo Ma, Jiaxi Xu, Jingjing Liu, Jun He, Tong Chang, Qingbiao Yang, Ning Li, Dong Qian, Zhenjiang Li
Summary: H-bonding has achieved significant progress by utilizing an H-bond donor (HBD) and an H-bond acceptor (HBA). This study introduces a new type of organic ion pair that exhibits cooperative catalytic effects. A new mechanism of H-bonding catalysis is proposed.
Article
Chemistry, Inorganic & Nuclear
Shui-Li Liu, Qi-Wei Chen, Zhen-Wei Zhang, Qing Chen, Lian-Qiang Wei, Ning Lin
Summary: In this study, two stable Fe(II) coordination compounds were synthesized and showed different catalytic activities when used for the Friedel-Crafts reaction. Compound 2 exhibited superior catalytic activity compared to 1 due to the coordination sites in Fe(II) facilitating intermediate formation and enhancing the electrophilic nature of beta-nitroalkenes. The high functional group and solvent tolerance of catalyst 2 allows for at least 3 times of recycling and reuse without significant loss of catalytic activity. This work presents a new strategy for the synthesis of indole alkaloids under ambient conditions.
JOURNAL OF SOLID STATE CHEMISTRY
(2022)
Article
Chemistry, Organic
James R. Frost, Choon Boon Cheong, Wasim M. Akhtar, Dimitri F. J. Caputo, Kirsten E. Christensen, Neil G. Stevenson, Timothy J. Donohoe
Summary: The study discusses the alkylation of ketones using 1 degrees or 2 degrees alcohols under hydrogen borrowing catalysis. Different substrates result in different alkylated products, with di-ortho-substituted aryl ketones being identified as a privileged scaffold. The research also explores diastereoselective and intramolecular hydrogen borrowing processes in the formation of beta-branched products.
Article
Chemistry, Organic
Takanori Shibata, Mio Sasaki, Masafumi Kojima, Mamoru Ito
Summary: The chiral Ir(I)-catalyzed intermolecular reaction of N-carbamoylpyrrole and indole derivatives with alpha,beta-unsaturated carbonyl compounds proceeded with high enantioselectivity, yielding chirally functionalized pyrroles and indoles as formal C-H conjugate adducts. The reaction mechanism was further investigated through deuterium labeling experiments.
Article
Chemistry, Multidisciplinary
Chihong Zhang, Zhen Zhang, Deliang Wang, Wenkun Wang, Bo Jin, Tao Wen, Lihua Ye, Zhong-Ning Chen, Hu Cai
Summary: In this study, we developed an efficient method for synthesizing diverse quinoxalines using the DMSO/(BuONa)-Bu-t/O-2 system as a single-electron oxidant. The method involves the formation of alpha-imino radicals and nitrogen radicals, which directly construct C-N bonds. This approach offers a novel way to generate alpha-imino radicals with high reactivity.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Guangcai Xu, Gerrit J. Poelarends
Summary: The application of biocatalysis in challenging synthesis has greatly benefited from the development of new enzymes. By incorporating catalysis modes from synthetic chemistry, novel biocatalysts have been created, and the design of iminium catalysis plays a fundamental role in this process. It has been shown that repurposing existing enzymes or constructing artificial enzymes can promote valuable abiological transformations, demonstrating the power of combining chemomimetic biocatalyst design and directed evolution in generating new-to-nature enzymes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Esra Dundar, Cihangir Tanyeli
Summary: A series of chiral bifunctional squaramide organocatalysts were evaluated for their application in Friedel-Crafts alkylation of indoles, showing high enantioselectivity and moderate yields. This new asymmetric transformation provides a simple, efficient, clean, and environmentally friendly route for chemical synthesis.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Yao Yang, Yurong Sun, Wenliang Gao, Tao Yang
Summary: The dual-site synergistic effect in heterogeneous catalysis is intriguing but complex. It involves two spatially separated and functionally independent active sites for the adsorption and activation of at least two substrate molecules. This complexity becomes more challenging when the substrate molecules are large. In this study, the replacement of Al3+ with Co2+ in Al4B6O15 lattice creates unsaturated Co2+ (4-fold coordination) and oxygen vacancies (O-v). These dual sites, acting as Lewis acid and oxygen adsorption sites, synergistically catalyze the Friedel-Crafts alkylation reactions of nitro-substituted molecules and indole derivatives. The catalyst exhibits high durability and the addition of hydrogen further enhances its catalytic activity, providing a novel perspective on the development of dual-site catalysts.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Organic
Anup Biswas
Summary: The aza-Friedel-Crafts reaction allows for the efficient coupling of electron-rich aromatic systems with imines, facilitating the incorporation of aminoalkyl groups into the aromatic ring. This reaction offers a wide range of forming aza-stereocenters, which can be controlled by different asymmetric catalysts. This review highlights recent advances in asymmetric aza-Friedel-Crafts reactions mediated by organocatalysts and provides mechanistic insights into the origin of stereoselectivity.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Physical
Reuben B. Leveson-Gower, Gerard Roelfes
Summary: Friedel-Crafts alkylation and acylation reactions are important in synthetic and industrial chemistry. Researchers have expanded the application of these reactions through directed evolution and created bio-hybrid catalysts. This review summarizes these efforts and discusses future routes for more efficient and benign Friedel-Crafts reactions.
Article
Chemistry, Applied
David Svestka, Jan Otevrel, Pavel Bobal
Summary: Here we report an asymmetric organocatalyzed method for the Friedel-Crafts reaction between activated phenols and trihaloacetaldehydes. A screening of 41 compounds identified a catalyst structure based on 3,5-dinitrobenzamide of 9-amino-epi-cinchonidine as the lead catalytic molecule. Under optimized conditions, the catalyst provided trihalohydroxyalkylated adducts in good yields and with high enantiomeric ratios. The reaction scope was determined on 29 entries and several follow-up transformations of the enantioenriched products were accomplished.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Karolina Ogorzaly, Gabriela Jajko, Karol Wolski, Szczepan Zapotoczny, Martin Kubu, Wieslaw J. Roth, Barbara Gil, Waclaw Makowski
Summary: This study investigates the preparation of layered zeolite composites using surfactant solutions under different pH conditions. The results show that samples prepared under high alkalinity exhibit well-defined expanded interlayer distances and show higher catalytic activity during TEOS treatment.
Article
Chemistry, Organic
Camilla Loro, Julie Oble, Francesca Foschi, Marta Papis, Egle M. Beccalli, Sabrina Giofre, Giovanni Poli, Gianluigi Broggini
Summary: Treatment of O-allyl N-tosyl carbamates with aromatic compounds in the presence of Cu(OTf)(2) or TMSOTf as promoters results in the formation of N-substituted 1-arylpropan-2-amines, 1,2-diarylpropanes, 1,1-diarylpropanes, or indanes, depending on the nature of the promoter and aryl substrates. A proposed mechanism explains the outcome of these C-H based cascades, involving initial acid promoted decarboxylative/deamidative Friedel-Crafts allylation followed by protonation of the allylated arene.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Bei Zhou, Zhuang Ma, Asma M. Alenad, Carsten Kreyenschulte, Stephan Bartling, Matthias Beller, Rajenahally Jagadeesh
Summary: A general method for cobalt-catalysed CH-alkylation of indoles with alcohols is reported, which allows the easy synthesis of substituted and functionalized indoles in good yields. The resulting products are an interesting class of heterocyclic compounds widely used in organic synthesis and medicinal chemistry.
Article
Chemistry, Multidisciplinary
Hai-Hua Lu, Michael D. Martinez, Ryan A. Shenvi
Article
Chemistry, Organic
Hai-Hua Lu, Bettina Hinkelmann, Thomas Tautz, Jun Li, Florenz Sasse, Raimo Franke, Markus Kalesse
ORGANIC & BIOMOLECULAR CHEMISTRY
(2015)
Article
Chemistry, Multidisciplinary
Hai-Hua Lu, Sergey V. Pronin, Yevgeniya Antonova-Koch, Stephan Meister, Elizabeth A. Winzeler, Ryan A. Shenvi
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2016)
Article
Chemistry, Multidisciplinary
Hai-Hua Lu, Aruna Raja, Raimo Franke, Dirk Landsberg, Florenz Sasse, Markus Kalesse
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2013)
Review
Biochemistry & Molecular Biology
Markus Kalesse, Martin Cordes, Gerrit Symkenberg, Hai-Hua Lu
NATURAL PRODUCT REPORTS
(2014)
Article
Chemistry, Organic
Hai-Hua Lu, Fu-Gen Zhang, Xiang-Gao Meng, Shu-Wen Duan, Wen-Jing Xiao
Article
Chemistry, Organic
Fu-Gen Zhang, Qing-Qing Yang, Jun Xuan, Hai-Hua Lu, Shu-Wen Duan, Jia-Rong Chen, Wen-Jing Xiao
Article
Chemistry, Organic
Shu-Wen Duan, Hai-Hua Lu, Fu-Gen Zhang, Jun Xuan, Jia-Rong Chen, Wen-Jing Xiao
SYNTHESIS-STUTTGART
(2011)
Article
Chemistry, Organic
Meng-Yue Cao, Zhi-Min Xu, Wei Gao, Juan Liu, Fen Tan, Hai-Hua Lu
Article
Chemistry, Multidisciplinary
Meng-Yue Cao, Bin-Jie Ma, Zhi-Qi Lao, Hongliang Wang, Jing Wang, Juan Liu, Kuan Xing, Yu-Hao Huang, Kang-Ji Gan, Wei Gao, Huaimin Wang, Xin Hong, Hai-Hua Lu
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Organic
Hai-Hua Lu, Meng-Yue Cao
Summary: The highly efficient and enantioselective palladium-catalyzed decarboxylative dearomative asymmetric allylic alkylation of benzofurans was achieved using new Trost-type bisphosphine ligands bearing a chiral cycloalkane framework. This led to a diversity-oriented synthesis of previously unreachable flavaglines, establishing a new avenue for developing drugs based on flavaglines.
Article
Chemistry, Multidisciplinary
Meng-Yue Cao, Bin-Jie Ma, Qing-Xiu Gu, Bei Fu, Hai-Hua Lu
Summary: This paper reports a concise protecting-group-free total synthesis of Daphenylline, a structurally unique member of the triterpenoid Daphniphyllum natural alkaloids. Key reactions include an intramolecular oxidative dearomatization reaction, a tandem reductive amination/amidation double cyclization reaction, and a highly enantioselective rhodium-catalyzed hydrogenation reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Hai-Hua Lu, Kang-Ji Gan, Fu-Qiang Ni, Zhihan Zhang, Yao Zhu
Summary: The concise total synthesis of salimabromide was achieved using a series of novel reactions, which allowed for the construction of its unique carbon skeleton and stereocenters.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Wenchao Chen, Esther Cai Xia Ang, Siu Min Tan, Zhijie Chua, Jingyun Ren, Ziqi Yang, Bo Teng, Richmond Lee, Haihua Lu, Choon-Hong Tan
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)