Article
Chemistry, Organic
Subarna Pan, Suparna Kundu, Rajarshi Samanta
Summary: This article describes a simple and efficient method for the synthesis of N-arylated 2-pyridone derivatives catalyzed by Rh(II), using 2-oxypyridine and diazonaphthoquinone as coupling partners. The reaction involves the insertion of the nitrogen atom of the 2-oxypyridine derivative into quinoid carbene and subsequent 1,6-benzoyl migratory rearrangement. The reaction exhibits broad scope and has the potential to provide axially chiral N-arylated 2-pyridone derivatives under suitable asymmetric conditions.
Article
Chemistry, Organic
Oliver M. Griffiths, Henrique A. Esteves, Yiding Chen, Karin Sowa, Oliver S. May, Peter Morse, David C. Blakemore, Steven Ley
Summary: Executing photoredox reactions in flow can improve reaction concentration, reduce reaction time, achieve better yields, facilitate catalyst preparation, and expand substrate scope, demonstrating broad applicability.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
You Wang, Yuli He, Shaolin Zhu
Summary: Migratory cross-coupling via metal migration is a significant process in academic and industrial fields, providing an attractive alternative for the synthesis of challenging structures. This Account outlines recent progress and developments in the field, including migration-functionalization modes, diverse functionalizations, and strategies for regio- and stereocontrol.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Wang Yao, Gaoyuan Zhao, Yue Wu, Lin Zhou, Upasana Mukherjee, Peng Liu, Ming-Yu Ngai
Summary: This research reports a strategy using excited-state palladium catalysis for the 1,2-radical migratory Mizoroki-Heck reaction, enabling C2-alkenylation of carbohydrates with 1-bromosugars and alkenes. The reaction shows tolerance to various functional groups and complex molecular architectures and expands the reactivity profile of excited-state Pd catalysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Itsuki Nohira, Naoto Chatani
Summary: In this study, a Ni-catalyzed cross-electrophile coupling between C(sp(2))-F bonds in ortho-fluoro-substituted aromatic amides and C(sp(2))-Cl bonds in aryl chlorides was reported. The reaction, using Zn as a reductant and (LiOBu)-Bu-t as a base, with LiCl and ZnCl2 as additives, displayed excellent functional group tolerance and a broad substrate scope. Furthermore, the reaction was also applicable to cross-electrophile coupling between C(sp(2))-F and C(sp(2))-O bonds in an aryl tosylate and a triflate derivative.
Article
Chemistry, Multidisciplinary
Xiaoli Jiang, Feng-Tao Sheng, Yao Zhang, Gao Deng, Shaolin Zhu
Summary: Designing ligands in transition-metal catalyzed reactions is challenging. In this study, researchers applied the concept of combining multiple ligands to enhance catalytic efficiency and selectivity. As a result, they successfully achieved asymmetric remote hydroacylation and migratory acylation reactions to synthesize chiral α-aryl ketones.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Cristian Cavedon, Sebastian Gisbertz, Susanne Reischauer, Sarah Vogl, Eric Sperlich, John H. Burke, Rachel F. Wallick, Stefanie Schrottke, Wei-Hsin Hsu, Lucia Anghileri, Yannik Pfeifer, Noah Richter, Christian Teutloff, Henrike Mueller-Werkmeister, Dario Cambie, Peter H. Seeberger, Josh Vura-Weis, Renske M. van der Veen, Arne Thomas, Bartholomaus Pieber
Summary: We demonstrate visible-light-mediated carbon-heteroatom cross-coupling reactions using a photoactive Ni(II) precatalyst. The activation of this precatalyst involves an initial intraligand charge transfer event triggered by visible light irradiation. Additionally, a porous, recyclable organic polymer for heterogeneous nickel catalysis of cross-coupling reactions is obtained through ligand polymerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Vilija Kederiene, Jolanta Rousseau, Marie Schuler, Algirdas Sackus, Arnaud Tatibouet
Summary: This study explores the use of carbohydrate anchored 1,3-oxazolidine-2-thiones (OZTs) for copper-catalyzed C-S bond formation with aryl iodides. Chemoselective S-arylation was achieved using copper iodide and dimethylethylenediamine (DMEDA) as the best ligand in dioxane at 60-90 degrees C. The resulting chiral oxazolines were obtained with reasonable to good yields under mild reaction conditions. This approach, which utilizes inexpensive transition metals and exhibits tolerance towards various functional groups, is a valuable strategy for obtaining S-substituted furanose-fused OZTs.
Article
Chemistry, Organic
Angel Renteria-Gomez, Macayla Guerrero, Mireya Ramirez-Lopez, Osvaldo Gutierrez
Summary: Fluoroalkylated compounds play significant roles in various fields, and the dicarbofunctionalization of alkenes is an efficient method for rapid compound construction and diversification. This study presents the first iron-catalyzed three-component fluoroalkylarylation of enamides, using selective formation and trapping of radicals under mild conditions and fast reaction times, providing an efficient synthetic route to build molecular complexity.
Article
Chemistry, Multidisciplinary
Xiaomin Shu, De Zhong, Yanmei Lin, Xiao Qin, Haohua Huo
Summary: We report a general and modular approach for the direct enantioselective alpha-arylation of saturated azacycles and acyclic N-alkyl benzamides via nickel/photoredox dual catalysis. This method requires no oxidants or organometallic reagents, features broad substrate scope and high enantioselectivities, and is applicable to late-stage diversification of medicinally relevant complex molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Gaoyuan Zhao, Wang Yao, Jaclyn N. Mauro, Ming-Yu Ngai
Summary: The study presents the first excited-state palladium-catalyzed 1,2-spin-center shift reaction for site-selective functionalization of carbohydrates. The strategy offers mild reaction conditions with high levels of selectivity, tolerating a wide range of functional groups and complex molecular architectures, suggesting a general approach for the rapid generation of natural and unnatural carbohydrates.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(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, Physical
Oleg V. Khazipov, Konstantin E. Shepelenko, Safarmurod B. Soliev, Ksenia A. Nikolaeva, Victor M. Chernyshev, Valentine P. Ananikov
Summary: This article presents a new efficient method for the C(2)-H arylation of (benz)imidazoles and (benz)oxazoles with aryl chlorides and aryl bromides under Ni/NHC catalysis, offering a user-friendly alternative to toxic phosphine ligands or unstable catalysts. By mapping a competitive picture of catalyst dynamics, a highly efficient catalytic system can be built under simple conditions for stabilization of catalytically active species.
Article
Chemistry, Organic
Zuyao Sun, Weitao Yan, Lihuang Xie, Wenchao Liu, Chunfa Xu, Fen-Er Chen
Summary: This article describes an efficient and stereoretentive copper-catalyzed cross-coupling reaction of glycosyl thiosulfonate and boronic acid for the construction of thioglycosides. The good functional group compatibility of this method enables the preparation of various bioactive aryl/alkenyl thioglycosides, including the hSGLT1 inhibitor.
Article
Chemistry, Organic
Yang Zhang, Dan Ye, Lei Shen, Kangjiang Liang, Chengfeng Xia
Summary: A photochemical protocol is developed for the synthesis of chiral 3-hydroxyoxindoles by coupling diarylamines and alpha-ketoesters using tandem photoredox and chiral phosphoric acid catalysis. The chiral phosphoric acid plays a crucial role in controlling the stereochemistry of the downstream radical-radical cross-coupling process.
Article
Chemistry, Multidisciplinary
Yue Fu, Emily E. Zerull, Jennifer M. Schomaker, Peng Liu
Summary: Ag-catalyzed nitrene transfer reactions are important for converting C-H bonds into C-N bonds with diverse selectivity. Computational studies help understand the factors influencing reaction selectivity and provide insights for rational catalyst and precursor selection for regiodivergent amination reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Amit Kumar Simlandy, Warabhorn Rodphon, Turki M. Alturaifi, Binh Khanh Mai, Hui-Qi Ni, John A. Gurak Jr, Peng Liu, Keary M. Engle
Summary: A redox-neutral catalytic coupling of nitroalkanes and unactivated alkenes is reported in this study, which proceeds by a directed carbopalladation mechanism. The combination of PdI2 as the precatalyst and HFIP solvent enables the reaction uniquely. Structurally complex nitroalkane products, including nitro-containing carbo- and heterocycles, can be prepared under convenient conditions without the use of toxic or corrosive reagents. The reaction mechanism is examined through deuterium labeling experiments and isolation of a catalytically relevant intermediate. Different catalytic activation modes are utilized to demonstrate orthogonal methods for site-selective functionalization of a polyfunctional nitroalkyl ketone. Density functional theory (DFT) calculations reveal that the carbopalladation transition state is stabilized by a Na·I interaction and H·I hydrogen bond with HFIP.
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, Multidisciplinary
Changmin Xie, Jacob Kim, Binh Khanh Mai, Shixuan Cao, Rong Ye, Xin-Yi Wang, Peng Liu, Ohyun Kwon
Summary: This research describes a catalytic asymmetric reaction for the synthesis of chiral compounds using specific oxidants and reductants. The reaction is conducted under mild conditions and exhibits a wide substrate scope, high yield, and excellent enantioselectivity. The study also demonstrates the effectiveness of the designed catalyst and successfully synthesizes seven biologically active compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Tobias Koengeter, Can Qin, Binh Khanh Mai, Qinghe Liu, Yucheng Mu, Peng Liu, Amir H. Hoveyda
Summary: This paper presents a stereoretentive strategy for catalytic cross-metathesis reaction between tri-, Z- or E-di, or monosubstituted olefins and Z- or E-2-bromo-2-butene, leading to the formation of various trisubstituted alkenyl bromides. The method is applicable for the generation of products containing polar moieties or sterically hindered alkenes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Amit Kumar Simlandy, Turki M. Alturaifi, Johny M. Nguyen, Lucas J. Oxtoby, Quynh Nguyen Wong, Jason S. Chen, Peng Liu, Keary M. Engle
Summary: We report a transient directing group (TDG) strategy for site-selective palladium-catalyzed reductive Heck-type hydroalkenylation and hydroalkynylation of alkenylaldehydes using alkenyl and alkynyl bromides. This strategy allows for the construction of a stereocenter at the delta-position with respect to the aldehyde. Computational studies reveal the beneficial roles of rigid TDGs, such as L-tert-leucine, in promoting TDG binding and inducing high levels of enantioselectivity in alkene insertion.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hui-Qi Ni, Malkanthi K. Karunananda, Tian Zeng, Shenghua Yang, Zhen Liu, K. N. Houk, Peng Liu, Keary M. Engle
Summary: Multistep organic synthesis allows the conversion of simple chemical feedstocks into more complex products with specific functions. This study introduces a novel approach to organic reactions that can generate multiple valuable products with different carbon skeletons in a single operation. Through a palladium-catalyzed reaction, a single alkene starting material can be converted into two structurally distinct products, demonstrating the potential for simultaneous access to diverse compounds. The findings of this study provide insights into the mechanistic details of this unique catalytic system and establish a new method for small-molecule library synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jingfeng Huo, Yue Fu, Melody J. Tang, Peng Liu, Guangbin Dong
Summary: In this research, the first nickel-catalyzed Catellani-type annulation of aryl triflates and chlorides was achieved to form various benzocyclobutene-fused norbornanes in high efficiency. Mechanistic studies revealed an unexpected outer-sphere concerted metalation/deprotonation pathway and the essential roles of the base and the triflate anion. Compared to palladium catalysis, the reaction showed a broad functional group tolerance and enhanced regioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jicheng Wu, Peijing Jia, Rositha Kuniyil, Peng Liu, Weiping Tang
Summary: In this study, we report an efficient method for the stereoselective synthesis of challenging α-linked glycoconjugates using a Rh-II/chiral phosphoric acid (CPA)-cocatalyzed dynamic kinetic anomeric O-alkylation. By exploring various parameters of the cocatalytic system, we achieved excellent anomeric selectivity, excellent diastereoselectivity, broad substrate scope, and high efficiency for this glycosylation reaction. DFT calculations suggested that the anomeric selectivity was determined by steric interactions between the C2-carbon of the carbohydrate and the phenyl group of the metal carbenoid, while diastereoselectivity at the newly generated stereogenic center was influenced by π-π interactions with the C2-OBn substituent on the carbohydrate substrate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Dennis A. Kutateladze, Binh Khanh Mai, Yuyang Dong, Yu Zhang, Peng Liu, Stephen L. Buchwald
Summary: A copper hydride-catalyzed approach has been developed for the synthesis of Z-configured trisubstituted alkenes with high stereo- and regioselectivity. This method provides a valuable strategy for accessing challenging classes of alkenes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Lei Cheng, Dian Li, Binh Khanh Mai, Zhiyu Bo, Lida Cheng, Peng Liu, Yang Yang
Summary: The merger of photoredox catalysis and PLP biocatalysis enables the development of a new synthetic method for preparing valuable noncanonical amino acids, allowing controlled formation of chiral products.
Article
Chemistry, Physical
Wenzhen Fu, Natalia M. M. Neris, Yue Fu, Yunlong Zhao, Benjamin Krohn-Hansen, Peng Liu, Yang Yang
Summary: This study describes a metalloredox biocatalysis strategy to repurpose natural cytochromes P450 for catalysing asymmetric radical cyclization to arenes through an unnatural electron transfer mechanism. Directed evolution yielded a series of engineered P450 aromatic radical cyclases with complementary selectivities. The excellent tunability of this metalloenzyme family provides an exciting platform for utilizing free radical intermediates in asymmetric catalysis.
Article
Chemistry, Physical
Amit Kumar Simlandy, Warabhorn Rodphon, Turki M. Alturaifi, Binh Khanh Mai, Hui-Qi Ni, John A. Gurak, Peng Liu, Keary M. Engle
Summary: We report a redox-neutral catalytic coupling of nitroalkanes and unactivated alkenes that proceeds by a directed carbopalladation mechanism. The reaction is enabled by the combination of PdI2 as the precatalyst and HFIP solvent. Complex nitroalkane products, including nitro-containing carbo- and heterocycles, can be prepared under convenient conditions without the need for toxic or corrosive reagents.
Article
Chemistry, Multidisciplinary
Gaoyuan Zhao, Upasana Mukherjee, Lin Zhou, Yue Wu, Wang Yao, Jaclyn N. Mauro, Peng Liu, Ming-Yu Ngai
Summary: This study reports the first direct strategy to synthesize C2-ketonyl-2-deoxysugars, important carbohydrate mimetics, from 1-bromosugars and silyl enol ethers via an excited-state palladium-catalyzed 1,2-spin-center shift process. The reaction is step-economic, has a broad substrate scope, high functional group tolerance, and can be used in the late-stage functionalization of natural product- and drug-glycoconjugates.
