Article
Chemistry, Organic
Laura Carceller-Ferrer, Carlos Vila, Gonzalo Blay, M. Carmen Munoz, Jose R. Pedro
Summary: A valuable organocatalytic vinylogous Mannich reaction has been established between alkylidenepyrazolones and isatin-derived ketimines. The reaction was catalyzed by a squaramide organocatalyst, resulting in a range of aminooxindole-pyrazolone adducts with excellent outcomes, including high yields and selectivities.
Article
Chemistry, Organic
Laura Carceller-Ferrer, Aleix Gonzalez del Campo, Carlos Vila, Gonzalo Blay, M. Carmen Munoz, Jose R. Pedro
Summary: A diastereo- and enantioselective organocatalyticaldol reaction was developed for the synthesis of chiral tertiary alcohols bearing a trifluoromethyl group from alkylidenepyrazolones and trifluoromethylketones. Despite moderate yields, the reaction showed excellent diastereoselectivity and moderate to good enantioselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Hao-Dong Qian, Zhi-Heng Li, Shuang Deng, Chaochao Yao, Hua-Ming Xiang, Guang Xu, Zi-Qi Geng, Zihao Wang, Linfeng Chen, Chunrong Liu, Cuiju Zhu, Xiaotian Qi, Hao Xu
Summary: Distinct regio- and enantioselectivity control has been achieved in copper-catalyzed vinylogous and bisvinylogous propargylic substitution using a novel chiral N,N,P ligand. The developed method provides an efficient and selective approach to the synthesis of enantioenriched alkynyl unsaturated carbonyl compounds, with excellent functional group tolerance and broad substrate scope. The synthetic utility of the developed method is demonstrated by gram-scale synthesis and application to the enantioselective synthesis of challenging compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Physical
Srimanta Manna
Summary: Copper-catalyzed enantioselective borylative cyclization is a powerful tool for generating boron-containing carbocycles and heterocycles through the difunctionalization of unsaturated hydrocarbons. This review focuses on the copper-catalyzed borofunctionalization and enantioselective cyclization of alkenes, allenes, and alkynes, as well as the current understanding of the underlying mechanisms.
Article
Chemistry, Applied
Santosh J. Gharpure, Rupali S. Chavan, Ajaykumar Ardhapure
Summary: This method allows for the stereoselective synthesis of various substituted tetrahydrofurans, tetrahydropyrans, and chromans using palladium catalyzed intramolecular radical cyclization, with broad substrate scope and applicability for gram-scale synthesis under suitable solvent conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Hou-Lu Liu, Xinyu Wang, Ke Gao, Zhaobin Wang
Summary: In this paper, we report a novel chromium-catalyzed asymmetric cyclopropanation reaction using readily available gem-dihaloalkanes and terminal olefins as precursors. This method provides diverse functionalized chiral cyclopropanes. Mechanistic studies reveal a radical-polar crossover process in this catalytic reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Chaoran Xu, Jianglin Qiao, Shunxi Dong, Yuqiao Zhou, Xiaohua Liu, Xiaoming Feng
Summary: A new bimetallic catalytic system was established for efficient synthesis of chiral heterocycles. The system promoted asymmetric [4 + 3]-cycloaddition reaction, leading to various chiral 4,5-dihydro-1,3-dioxepines in yields up to 97% with 99% ee.
Article
Chemistry, Organic
Zhiqiang Zhou, Dongyang Xu, Wei Jiang, Junhan Chen, Yanxia Zhen, Jiyou Huo, Jiahang Yan, Jinming Gao, Weiqing Xie
Summary: In this study, a catalytic asymmetric intramolecular vinylogous aldol reaction using dual organocatalysts was described, allowing for the convergent synthesis of ortho-fused tricyclic diketones with excellent enantioselectivities and diastereoselectivities. Notably, the reaction selectively generates three consecutive stereogenic carbon centers, including a quaternary one. Density functional theory calculations revealed that the enhanced enantioselectivity was facilitated by a transannular hydrogen bonding between the protonated quinuclidine moiety of the chiral aminocatalyst and the diketone fragment of the substrate.
Article
Chemistry, Multidisciplinary
Yasutaka Tsuji, Kazumasa Kon, Takahiro Horibe, Kazuaki Ishihara
Summary: A chiral amidophosphate-N-iodosuccinimide cooperative catalysis has been developed for the site-, diastereo-, and enantioselective iodocyclization of 2-geranylarenols with molecular iodine to give iodo-containing polycyclic compounds with good selectivity. The catalytic system involves the formation of a reactive chiral iodonium species through dual halogen-bonding interactions with a chiral Lewis base and Lewis acid. The bulky 3,3'-substituents of the chiral BINOL-derived amidophosphate are crucial for inducing site-selective iodination at the less-hindered terminal alkenyl moiety of 2-geranylarenols.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Shu-Pei Yuan, Xia-Yan Zhang, Yun-Qing Jia, Zhen-Hua Wang, Jian-Qiang Zhao, Yong You, Ming-Qiang Zhou, Wei-Cheng Yuan
Summary: An efficient catalytic asymmetric coupling of vinylogous species is developed by adding deconjugated butenolide to vinylogous imines in situ generated from arylsulfonyl indoles. Using quinine-derived bifunctional squaramide as the catalyst, a series of structurally diverse enantioenriched sec-alkyl-3-substituted indoles containing valuable gamma,gamma-disubstituted butenolide moieties and adjacent quaternary-tertiary stereocenters are obtained with synthetically viable results (up to 97% yield, 77 : 23 dr and 97% ee).
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Tarun Nallamilli, Anandarao Munakala, Rambabu Chegondi
Summary: In this study, a novel cascade annulation reaction of enone-tethered cyclohexadienones was achieved by using a combined Lewis acid catalyzed halogenation reaction and trimethylsilyl halide. This method provides a highly efficient way to synthesize bicyclic enones with multiple stereocenters.
Article
Chemistry, Multidisciplinary
Santosh J. Gharpure, Dipak J. Fartade, Krishna S. Gupta, Raj K. Patel
Summary: The TMSOTf-mediated reaction of alkynyl vinylogous carbonates unexpectedly generates 1,4-oxazepine and dihydropyran dienes through the transposition of an ethyl acrylate moiety via an intramolecular cascade Prins-type cyclization/retro-oxa-Michael reaction/cycloisomerisation. This atom-economical protocol selectively produces a specific E double bond geometry, and the dihydropyran dienes can be further transformed into polycyclic heterocycles using the Heck reaction.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Oliver D. Jackson, Ksenia S. Stankevich, Matthew J. Cook
Summary: An auto-tandem catalytic, branched-selective rearrangement of substituted N-alloc-N-allyl ynamides was developed, which provides an easy access to complex quaternary nitrile products with vinylogous stereocentres in excellent diastereoselectivity, including contiguous all-carbon quaternary centres. The stereochemical outcome is determined via a Pd(0) catalysed dipolar ketenimine aza-Claisen rearrangement, and computational studies illustrate the significant role of ligand geometry.
CHEMICAL COMMUNICATIONS
(2022)
Review
Chemistry, Organic
Asha Budakoti, Pradip Kumar Mondal, Prachi Verma, Jagadish Khamrai
Summary: The Prins reaction is an important technique for the synthesis of tetrahydropyran skeletons with various substituents, and has been successfully applied in the total synthesis of bioactive macrocycles and related natural products.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Li Lin, Mei Wang, Jiawei Zhou, Fei Li, Huiyun Liu
Summary: The direct C2 addition of 5H-oxazol-4-ones to gamma-keto-alpha,beta-unsaturated esters catalyzed by a chiral squaramide has been achieved, resulting in diverse highly functionalized gamma-keto esters with a C2-oxazolone at the alpha-position in high yields and excellent stereoselectivities (d.r. > 20:1 and up to 98% ee).
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Feilong Sun, Jie Ni, Gui-Juan Cheng, Xianjie Fang
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Organic
Yi Deng, Chunyang Zhao, Yu Zhou, Hongwei Wang, Xuexiang Li, Gui-Juan Cheng, Junkai Fu
Article
Chemistry, Multidisciplinary
Xi-Tao Li, Ling Lv, Ting Wang, Qiang-Shuai Gu, Guo-Xing Xu, Zhong-Liang Li, Liu Ye, Xinhao Zhang, Gui-Juan Cheng, Xin-Yuan Liu
Article
Chemistry, Multidisciplinary
Jihui Gao, Mingdong Jiao, Jie Ni, Rongrong Yu, Gui-Juan Cheng, Xianjie Fang
Summary: A regiodivergent nickel-catalyzed hydrocyanation of a broad range of internal alkenes with high regioselectivities is reported, achieving either linear or branched nitriles with good yields. DFT calculations showed that the catalyst architecture plays a crucial role in determining regioselectivity by modulating electronic and steric interactions. Additionally, moderate enantioselectivities were observed in the production of branched nitriles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Chengxi Yang, Peng Li, Xiaoli Ding, Hao Chen Sui, Shun Rao, Chia-Hsiang Hsu, Wing-Por Leung, Gui-Juan Cheng, Pan Wang, Bao Ting Zhu
SCIENTIFIC REPORTS
(2020)
Article
Chemistry, Physical
Liqun Hu, Yibing Liu, Xiong Fang, Yuzhu Zheng, Rong-zhen Liao, Man Li, Youwei Xie
Summary: An activation mode for unactivated alkenes using Re2O7/HReO4 and hexafluoroisopropanol (HFIP) was described. This method enables the intermolecular hydroarylation of highly electron-deficient styrenes with various arenes, leading to the synthesis of a variety of diarylalkanes in high efficiency. The reaction conditions are mild, the substrate scope is broad, and the yields are high, with minimal waste generation. The importance of HFIP in reducing the energy barriers for key steps of the transformation was confirmed through DFT calculations and deuterium-labeling experiments.
Review
Chemistry, Multidisciplinary
Sunggi Lee, Won-jin Chung
Summary: This review provides an overview of the development and application of asymmetric phase-transfer catalysis (PTC) in enantioselective halogenations over the past decade. By utilizing highly ordered ion pairing and hydrogen-bonding interactions, electrophilic and nucleophilic reactions are enabled through a carefully designed chiral phase-transfer catalyst, leading to successful results in fluorination and with heavier halogens.
BULLETIN OF THE KOREAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Jaehan Bang, Seyun Gi, Yoonjung Lee, Kian L. Tan, Sunggi Lee
Summary: This study describes the meta-selective C-H functionalization of arylsilanes using a Si-tethered directing group. The method allows for selective alkenylation of arenes with various functional groups, including electron-deficient olefins. Further functional group transformations of the silicon-tethered directing group efficiently produce multi-substituted arenes.
Article
Chemistry, Multidisciplinary
Yujeong Lee, Guilherme L. Tripodi, Donghyun Jeong, Sunggi Lee, Jana Roithova, Jaeheung Cho
Summary: A high-valent manganese(IV)-hydroxo complex was synthesized and characterized in this study. It was found that this complex can activate C-H bonds of aliphatic and aromatic compounds under mild conditions. Detailed kinetic studies revealed that the activation of C-H bonds occurs via rate-determining hydrogen atom abstraction and electron-transfer pathway.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Yibing Liu, Liqun Hu, Yuzhu Zheng, Xiong Fang, Youwei Xie
Summary: This publication describes the use of Re2O7 in HFIP to activate inert and electronically deactivated olefins for a challenging intramolecular hydroacyloxylation reaction. Both HFIP and an internal carboxy group are crucial for the successful implementation of this transformation, as they assist in the formation and stabilization of the key cationic intermediate through hydrogen-bonding interactions with ReO4-.
Article
Chemistry, Multidisciplinary
Duohang Bi, Fei Qu, Wanyue Xiao, Jiaxin Wu, Pei Liu, Hongyao Du, Youwei Xie, Hongmei Liu, Lianbin Zhang, Juan Tao, Yijing Liu, Jintao Zhu
Summary: This study developed detachable H2O2-responsive gel-based microneedle (MN) patches containing methotrexate (MTX) and epigallocatechin gallate (EGCG), which showed dual-mode drug release kinetics and improved treatment outcomes in psoriasis-like animal models. The gel-based MNs extended skin retention of EGCG, leading to prolonged ROS scavenging effects. These ROS-responsive MN patches delivered antiproliferative and anti-inflammatory drugs transdermally, demonstrating potential for improved psoriasis treatment.
Article
Chemistry, Inorganic & Nuclear
Kyungmin Kim, Seongmin Oh, Donghyun Jeong, Yuri Lee, Dohyun Moon, Sunggi Lee, Jaeheung Cho
Summary: In this study, a series of cobalt(III)-peroxo complexes and cobalt(III)-hydroperoxo complexes were synthesized and characterized. The results showed that their structures and properties were influenced by the electronic effects of the ligands, providing important insights into the electronic nature-reactivity relationship of metal-oxygen species.
INORGANIC CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Hongmei Liu, Qing Huang, Rong-zhen Liao, Man Li, Youwei Xie
Summary: In this article, the authors challenge the traditional mechanism of transetherification between ethers and alcohols by using Re2O7-mediated annulation. They demonstrate that the activation of the alcohol hydroxy group followed by nucleophilic attack of the ether, instead of ether activation, is the primary step in this reaction. This alternative mechanism is suitable for substrates with multiple ether moieties, which is unprecedented in previous methods.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Somi Kim, Junhyuk Jo, Sunggi Lee, Won-jin Chung
Summary: In this report, stereochemical modulation was achieved by utilizing pyridine-boryl radical to leave a synthetically modifiable boronate moiety during the cyclization step, leading to a successful catalytic synthesis of trans-2-substituted-1-indanols.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Yuzhu Zheng, Xiong Fang, Wen-Hao Deng, Bin Zhao, Rong-Zhen Liao, Youwei Xie
Summary: This manuscript presents a general method for the intramolecular dehydrative Friedel-Crafts reaction of alcohols catalyzed by Re2O7. The optimized conditions allow for efficient synthesis of various pharmaceutically important organic scaffolds. The potential application of this method is demonstrated through the synthesis of several commercially available drugs or biologically relevant molecules. DFT calculations suggest that Re2O7 prefers activation of hydroxyl groups through ester formation and heterolytic cleavage of C-O bonds.
ORGANIC CHEMISTRY FRONTIERS
(2022)
