Article
Chemistry, Organic
Yang Hong, Meng-Yuan Dong, Dong-Sheng Li, Hong-Ping Deng
Summary: This article reports a general and mild strategy for three-component carboarylation of unactivated alkenes with protic C(sp3)-H feedstocks via photoredox catalysis. The catalytic system is compatible with a broad range of unactivated alkenes, cyano-substituted arenes, and diverse protic C(sp3)-H feedstocks. The synthetic value of this method was demonstrated by late-stage functionalization of complex molecules and the synthesis of antiallergies including pheniramine, chlorpheniramine, and brompheniramine.
Article
Chemistry, Organic
Hai-Bin Yang, Xiao-Fang Jin, Hui-Ying Jiang, Wenwei Luo
Summary: A C(sp2)-C(sp2) bond was formed through a photoredox/N-heterocyclic carbene (NHC)-catalyzed radical cross-coupling reaction, presenting an alternative approach to traditional electron pair processes. This method demonstrated the first example of an NHC-catalyzed two-component radical cross-coupling reaction involving C(sp2)-centered radical species. The decarboxylative acylation of oxamic acid with acyl fluoride proceeded under mild conditions, enabling the synthesis of various useful alpha-keto amides, including sterically congested compounds.
Article
Chemistry, Multidisciplinary
Jing Cao, Joshua L. Zhu, Karl A. Scheidt
Summary: In this study, a cerium-catalyzed acylation reaction was reported, which can acylate unactivated C(sp3)-H bonds under mild and operationally-friendly conditions. The reaction shows excellent generality, accommodating a wide range of feedstock chemicals, and facilitating the late-stage functionalization of pharmaceuticals.
Review
Chemistry, Multidisciplinary
Cheng-Long Ji, Xinyi Zhai, Qing-Yun Fang, Chengjian Zhu, Jie Han, Jin Xie
Summary: In recent years, the activation of unactivated alkyl chlorides through light-induced processes has become a promising field in radical chemistry, allowing for the easy construction of carbon-carbon and carbon-heteroatom bonds. Recent studies in medicinal chemistry show that their presence is associated with high success rates in clinical trials. This review summarizes the recent advances in the photoinduced activation of unactivated alkyl chlorides and discusses the underlying mechanistic aspects, aiming to inspire developments in organic chemistry, drug synthesis, materials science, and related disciplines.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Multidisciplinary Sciences
Shuaishuai Wang, Tingrui Li, Chengyihan Gu, Jie Han, Chuan-Gang Zhao, Chengjian Zhu, Hairen Tan, Jin Xie
Summary: This article reports on an iron-catalyzed reaction for efficient construction of aromatic tertiary amines, which is important in drug discovery and organic chemistry. The reaction employs a radical tandem C-N coupling strategy and can synthesize nonsymmetric aromatic tertiary amines under mild conditions.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Su Chen, Luc Van Meervelt, Erik V. Van der Eycken, Upendra K. Sharma
Summary: A mild visible-light-driven palladium-catalyzed radical tandem dearomatization reaction of indoles with unactivated alkenes is described. This reaction exhibited moderate to good yields and good to excellent diastereoselectivities. Under visible-light irradiation, a photo-excited state of the palladium complex was formed, which enabled the transfer of a single electron to N-(2-bromobenzoyl)indoles, leading to a hybrid palladium radical chemistry. This approach provides efficient and atom-economical access to diverse 2,3-disubstituted indoline derivatives.
Article
Multidisciplinary Sciences
Caiyou Chen, Jonas C. Peters, Gregory C. Fu
Summary: The study describes a method for enantioselective substitution of unactivated alkyl electrophiles using a copper-based photoinduced catalyst system, expanding the scope of enantioselective N-substitution reactions to include unactivated electrophiles.
Article
Chemistry, Multidisciplinary
Heejun Lee, Jun Myun Ahn, Paul H. Oyala, Cooper Citek, Haolin Yin, Gregory C. Fu, Jonas C. Peters
Summary: Photoinduced, copper-catalyzed couplings of nitrogen nucleophiles with alkyl electrophiles have been shown to be an attractive approach for achieving enantioselective C-N bond formations. This study provides mechanistic insight into a previously reported photoinduced, copper-catalyzed enantioconvergent C-N coupling. Experimental and computational results support the proposed intermediates and their chemical stability and competence in producing the desired C-N coupling product with enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Xin-Yang Lv, Ruben Martin
Summary: Here, the development of a copper-catalyzed C-(sp(3)) amination of unactivated secondary alkyl iodides mediated by diaryliodonium salts is described. The method involves the intermediacy of aryl radical species that undergo halogen atom transfer prior to interfacing with copper catalysts, enabling the formation of C-N bonds at sp(3)-hybridized carbons. The protocol is characterized by its mild reaction conditions, excellent regioselectivity, and wide substrate scope.
Article
Multidisciplinary Sciences
Leipeng Xie, Shenghao Wang, Lanlan Zhang, Lei Zhao, Chun Luo, Linping Mu, Xiuguang Wang, Chao Wang
Summary: The authors presented a method to add aryl and amino groups to alkenes regio- and diastereoselectively via nickel catalysis and a removable directing group. This method enables high levels of regio-, chemo- and diastereocontrol, and is compatible with broad substrate scope and high functional group tolerance. The utility of this method in site-selective modification of pharmaceutical agents has been demonstrated.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Mingjie Liu, Junnan Liu, Jing Li, Zhenghua Zhao, Kai Zhou, Yueming Li, Peipei He, Jiashu Wu, Zongbi Bao, Qiwei Yang, Yiwen Yang, Qilong Ren, Zhiguo Zhang
Summary: This study demonstrates a novel strategy to address the limitations of aryl-ketone photocatalysts in terms of photostability and photoinduced electron transfer applications. By incorporating symmetric aryl ketones into conjugated covalent organic frameworks, improvements in photostability, electronic transfer efficiency, and structure-performance relationships were observed. This system provides a robust rule of thumb for designing new-generation aryl-ketone photocatalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Sean M. M. Treacy, Daniel R. R. Vaz, Syed Noman, Cedric Tard, Tomislav Rovis
Summary: gamma-Lactams, which are commonly found in small-molecule pharmaceuticals, can be used as precursors for highly substituted pyrrolidines. Previously, redox approaches to gamma-Lactam synthesis required additional electron withdrawing functionality and N-aryl substitution to promote electrophilicity and prevent undesired reactions. However, a new strategy using alpha-bromo imides and alpha-olefins enables the synthesis of monosubstituted protected gamma-Lactams in a formal [3 + 2] fashion, offering opportunities for further derivatization.
Article
Chemistry, Multidisciplinary
Bin Sun, Rongcheng Shi, Kesheng Zhang, Xiaoli Tang, Xiayue Shi, Jiayun Xu, Jin Yang, Can Jin
Summary: A novel and green strategy for the synthesis of acylated quinazolinone derivatives has been developed, using a photo-induced decarboxylative cascade radical acylation/cyclization reaction. The reaction proceeds smoothly without the need for external photocatalysts, additives, or oxidants, and can be easily scaled-up under flow conditions with sunlight irradiation.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Hangcheng Ni, Chaoming Li, Xingzi Shi, Xianyue Hu, Hui Mao
Summary: The combination of ligand-to-metal charge transfer radical chemistry and metal catalysis enables visible-light-promoted N-H alkylation of amides and N-heterocycles, producing a wide variety of N-alkylated products. The applicability of this method is further demonstrated through late-stage alkylation of N-H-containing pharmaceuticals. A mechanistic study reveals the key role of hydrogen atom transfer in activating C(sp(3))-H precursors.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Can-Can Zhang, Hong-Li Wu, Xuan-Chi Yu, Ling-Tao Wang, Yu Zhou, Yong-Bin Sun, Wen-Ting Wei
Summary: The combination of photo and copper catalysts can accelerate chemical synthesis and achieve aminoalkylation reactions. This strategy allows the generation of a broad range of functionalized nitrogenous molecules in the absence of an external photosensitizer and base. The reaction proceeds through a photoinduced complex species of nitrogen nucleophiles, intermolecular radical addition, and hydrogen atom transfer processes, as investigated by control experiments and theoretical tests.
Article
Chemistry, Multidisciplinary
Haolin Yin, Gregory C. Fu
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Correction
Chemistry, Multidisciplinary
Agnieszka Bartoszewicz, Carson D. Matier, Gregory C. Fu
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Multidisciplinary Sciences
Haohua Huo, Bradley J. Gorsline, Gregory C. Fu
Article
Chemistry, Multidisciplinary
Ze-Peng Yang, Gregory C. Fu
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Multidisciplinary
Zhaobin Wang, Ze-Peng Yang, Gregory C. Fu
Summary: The development of efficient methods, particularly catalytic and enantioselective processes, for the construction of all-carbon quaternary stereocentres is an important and difficult challenge in organic synthesis. A nickel-based chiral catalyst has been shown to achieve enantioconvergent couplings of tertiary electrophiles with alkenylmetal nucleophiles, providing access to a variety of organic compounds with good yield and enantioselectivity. This approach offers a potentially versatile strategy for the synthesis of complex molecules, including natural product intermediates.
Article
Chemistry, Multidisciplinary
Ze-Peng Yang, Dylan J. Freas, Gregory C. Fu
Summary: Chiral dialkyl carbinamines are important compounds in various fields, and two mild methods for their catalytic enantioconvergent synthesis using a chiral nickel catalyst have been reported. These methods are versatile and can be used for the synthesis of a variety of functionalized dialkyl carbinamines, including a one-pot variant for generating enantioenriched compounds from commercially available amino acid derivatives. The utility of these methods has been demonstrated in the efficient catalytic enantioselective synthesis of a range of target molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Ze-Peng Yang, Dylan J. Freas, Gregory C. Fu
Summary: Interest in unnatural alpha-amino acids has grown rapidly in recent years, and developing efficient methods for their enantioselective synthesis is a key objective. The use of a nickel-based chiral catalyst has enabled the enantioconvergent coupling of racemic alkyl electrophiles with alkylzinc reagents, yielding protected unnatural alpha-amino acids. This novel cross-coupling method has successfully produced enantioenriched unnatural alpha-amino acids for the synthesis of bioactive compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Multidisciplinary Sciences
Caiyou Chen, Jonas C. Peters, Gregory C. Fu
Summary: The study describes a method for enantioselective substitution of unactivated alkyl electrophiles using a copper-based photoinduced catalyst system, expanding the scope of enantioselective N-substitution reactions to include unactivated electrophiles.
Article
Chemistry, Multidisciplinary
Heejun Lee, Jun Myun Ahn, Paul H. Oyala, Cooper Citek, Haolin Yin, Gregory C. Fu, Jonas C. Peters
Summary: Photoinduced, copper-catalyzed couplings of nitrogen nucleophiles with alkyl electrophiles have been shown to be an attractive approach for achieving enantioselective C-N bond formations. This study provides mechanistic insight into a previously reported photoinduced, copper-catalyzed enantioconvergent C-N coupling. Experimental and computational results support the proposed intermediates and their chemical stability and competence in producing the desired C-N coupling product with enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Hyungdo Cho, Hidehiro Suematsu, Paul H. Oyala, Jonas C. Peters, Gregory C. Fu
Summary: Transition-metal catalysis of substitution reactions of alkyl electrophiles by nitrogen nucleophiles is an important strategy for synthesizing higher-order amines and controlling their stereochemistry. This study reports the photo-induced enantioconvergent coupling of racemic tertiary alkyl electrophiles with aniline nucleophiles using a readily accessible chiral copper catalyst. The mechanism of this catalytic process has been elucidated using various tools, leading to the identification of key copper-based intermediates in the proposed cycle.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Holden W. H. Lai, Francesco M. Benedetti, Jun Myun Ahn, Ashley M. Robinson, Yingge Wang, Ingo Pinnau, Zachary P. Smith, Yan Xia
Summary: A class of hydrocarbon ladder polymers with high selectivity and high permeability has been discovered, which shows great potential for industrial gas separations and exhibits desirable mechanical and thermal properties.
Article
Multidisciplinary Sciences
Caiyou Chen, Gregory C. C. Fu
Summary: Carbon-oxygen bonds are common in organic molecules, making methods for their construction with control of stereoselectivity important. The widely used Williamson ether synthesis has limitations in terms of scope and stereochemistry due to its reaction mechanism. Transition-metal catalysis has the potential to overcome these limitations but progress has been limited, especially in controlling enantioselectivity. We demonstrate that a readily available copper catalyst can achieve enantioconvergent substitution reactions of α-haloamides with oxygen nucleophiles, offering a promising solution to the challenge of enantioselective alkylations of heteroatom nucleophiles.
Article
Chemistry, Multidisciplinary
Xiaoyu Tong, Ze-Peng Yang, Carlos E. Del Angel E. Aguilar, Gregory C. Fu
Summary: This study reports an iron catalyst for cross-coupling reactions of alkyl electrophiles using olefins and hydrosilanes instead of alkylmetal reagents. Carbon-carbon bond formation occurs at room temperature, and the method utilizes commercially available components. Mechanistic studies suggest the generation of an alkyl radical from the alkyl electrophile and reversible elementary steps.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zhuo-Yan Wang, Dylan J. Freas, Gregory C. Fu
Summary: In this paper, a mild method for the synthesis of carbon-fluorine bonds by fluorination of hindered alkyl halides was reported. The method is simple and compatible with various functional groups.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)