Article
Chemistry, Organic
Xi Xiao, Xiaobiao Lu, Ming Zhang, Haoqing Hou, Changfeng Wan, Jinbiao Liu
Summary: A novel synthetic method was successfully developed for the preparation of multisubstituted dihydrochromeno[2,3-b]indole derivatives in moderate to high yields using a catalytic environmentally benign iron salt.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Haipeng Hu, Xin Wu, Yuqian Qiu, Cuilin Wang, Wei Wang, Guizhou Yue, Hanguang Wang, Juhua Feng, Guangtu Wang, Hailiang Ni, Ping Zou
Summary: In this study, the dehydrative mono-/dialkylation reactions of alcohols and beta-ketoacids were achieved under arylboronic acid catalysis, leading to the formation of beta-aryl ketones and beta-ketoesters in moderate to high yields. The reaction temperature was found to control the selectivity between decarboxylative alkylation and decarboxylation processes. A possible catalytic cycle was proposed based on experimental evidence.
Article
Chemistry, Organic
Fan Xiao, Peiqin Liao, Xiaoguang Lu, Jin Wang, Xiu-Qin Dong, Chun-Jiang Wang
Summary: In this study, an Ir-catalyzed asymmetric cascade reaction was successfully developed for the synthesis of chiral oxazinoindolone compounds with high efficiency. The method can be applied to pyrroles and other nitrogen-containing aromatic heterocycles. The reaction pathway was proposed based on preliminary mechanistic investigation. Importantly, the key intermediate for marine alkaloid (+)-agelastatin A can be readily accessed using this methodology.
Review
Chemistry, Multidisciplinary
Shenghan Teng, Jianrong Steve Zhou
Summary: This review summarizes the recent advances in transition metal-catalyzed asymmetric alkylation of heteroarenes using alkenes, covering literature from 2000 to late 2021. The reactions are classified into different categories based on the metal-mediated substrate activation, and the corresponding reaction mechanisms and catalyst design are discussed.
CHEMICAL SOCIETY REVIEWS
(2022)
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, 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, Physical
Iryna D. Alshakova, Martin Albrecht
Summary: This research presents an efficient catalytic cascade process for the synthesis of triarylmethanes using a novel iridium catalyst. The method achieves efficient C-C coupling through reductive Friedel-Crafts alkylation, with high yields, excellent selectivities, and low iridium loadings. The catalytic activity of the system with hydride-proton coordination is significantly higher than that of other systems, demonstrating high catalytic performance.
Article
Chemistry, Multidisciplinary
Xi-Jia Liu, Wen-Yun Zhang, Chao Zheng, Shu-Li You
Summary: Herein, an Ir-catalyzed asymmetric allylic substitution reaction of methyl azaarenes is reported. The reaction exhibits high yields and enantioselectivity, and utilizes the Knochel reagent for the formation of benzylic nucleophiles without additional activating reagents. The synthetic utility of this method has been demonstrated by an enantioselective synthesis of an allosteric protein kinase modulator.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Woo-Ok Jung, Binh Khanh Mai, Brian J. Spinello, Zachary J. Dubey, Seung Wook Kim, Craig E. Stivala, Jason R. Zbieg, Peng Liu, Michael J. Krische
Summary: The systematic study of simple nitronate nucleophiles in iridium-catalyzed allylic alkylation demonstrates the synthesis of beta-stereogenic alpha-quaternary primary amines. DFT calculations reveal early transition states and distinct trans-effects of diastereomeric chiral-at-iridium pi-allyl complexes in facilitating the formation of congested tertiary-quaternary C-C bonds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Multidisciplinary Sciences
Xiang Pu, Qiu-Di Dang, Lei Yang, Xia Zhang, Dawen Niu
Summary: The authors report a doubly-stereoconvergent, Cu/Mg-catalyzed asymmetric propargylic substitution reaction that can selectively construct products with vicinal congested stereocenters. This reaction uses readily available starting materials, environmentally friendly catalysts, and has a broad substrate scope.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Pan Tang, You -Yuan Wei, Long Wen, Hao-Jie Ma, Yi Yang, Yan Jiang
Summary: This article investigates the MgI2-catalyzed nucleophilic ring-opening reactions of donor-acceptor cyclopropanes with indoline-2-thiones as sulfur nucleophiles. Under mild reaction conditions, a series of functionalized gamma-indolylthio butyric acid derivatives are obtained in good to excellent yields. Additionally, the thioether functionalized ring-opening products can be transformed into sulfone and methionine analogues.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jianguo Yang, Saimei Liu, Jing Gui, Daokai Xiong, Jinshan Li, Zhiming Wang, Jun Ren
Summary: A highly selective hydroxyalkylation of aniline derivatives with arylglyoxal hydrates has been achieved using HFIP as a catalyst. The reaction provides efficient synthesis of various N,N-dialkylanilines and their derivatives with alpha-hydroxy carbonyl units under mild conditions. The method has shown great synthetic potential by enabling the facile synthesis of several structurally interesting molecules.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jia-Le Zheng, Fei Liu, Xue Song, Zhi Zhao, Wei Du, Ying-Chun Chen
Summary: In this study, we found that dienones generated from the Morita-Baylis-Hillman carbonates of 2-cyclopentenone under Pd(0) catalysis could be umpolunged through pi-Lewis base activation to form regioselective eta 2-Pd(0) complexes, which then underwent asymmetric inverse-electron-demand oxa-Diels-Alder reaction with alpha-cyano chalcones. This study successfully constructed a range of fused pyran frameworks with dense substitutions and demonstrated excellent stereoselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yunlong Zhao, Rou Xiao, Weibin Fang, Junling Zhao
Summary: This study presents a protocol for the highly selective addition reaction of isatin-derived beta,gamma-unsaturated alpha-ketoesters with 4-aminoindoles at the C7 position. The reaction, catalyzed by a SPINOL-derived chiral phosphoric acid, yields bisindole derivatives with up to 97% enantiomeric excess. Further biological testing revealed that the products have high cytotoxicity against various cancer cell lines.
ORGANIC CHEMISTRY FRONTIERS
(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.
