Article
Chemistry, Organic
Qinyu Luo, Xiu Wang, Jinbo Hu
Summary: The introduction of fluorine atoms into a carbon-carbon double bond can significantly alter the physical, chemical, and biological properties of a target molecule. Fluorinated alkenes, which are important compounds widely used in medicinal chemistry and materials science, can be synthesized through the Julia and Julia-Kocienski reactions using a-fluorinated sulfones. This review summarizes the methods for synthesizing fluorinated alkenes through Julia and Julia-Kocienski reactions, categorizing them based on target molecules and sulfone reagents, and highlights the unique effect of fluorine substituents.
Review
Chemistry, Organic
Guna Sakaine, Zigmars Leitis, Rebeka Locmele, Gints Smits
Summary: This review summarizes the scientific literature of the past decade, focusing on the key aspects for successful execution of the olefination step. The main stereoselectivity and yield-determining aspects have been outlined, providing all the necessary information for the synthesis of Julia-Kocienski reagents as well as the most commonly used reaction optimization techniques.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Organic
Konstantinos A. A. Ouzounthanasis, Stergios R. R. Rizos, Alexandros E. E. Koumbis
Summary: The Julia-Kocienski olefination, a coupling reaction between a carbonyl component and a sulfone partner, has become an important tool in the synthetic toolbox for preparing various organic compounds. Recent studies have focused on the synthesis of trisubstituted alkenes and understanding their stereoselectivity. This review provides a comprehensive overview of the progress and developments in the application of Julia-Kocienski olefination for the synthesis of trisubstituted alkenes, which are valuable precursors for natural products, analogs, and biologically important compounds. The review also discusses key methodologies, optimal conditions, stereoselectivities, and new modifications and approaches.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Li-Xia Liu, Yu-Qing Bai, Xiang Li, Chang-Bin Yu, Yong-Gui Zhou
Summary: Combining base-promoted retro-sulfa-Michael addition with palladium-catalyzed asymmetric allenylic alkylation, a streamlined synthesis of chiral thiochromanones containing two central chiralities (including a quaternary stereogenic center) and an axial chirality (allene unit) was successfully achieved, with yields up to 98%, dr of 49.0:1, and >99% ee.
Article
Chemistry, Organic
Makoto Inai, Yoshinori Ueno, Hiroto Sagara, Hitoshi Ouchi, Fumihiko Yoshimura, Toshiyuki Kan
Summary: This study presents the first total synthesis of isosilybin B (4) and introduces a synthetic strategy that utilizes the modified Julia-Kocienski olefination reaction and the construction of a quinomethide intermediate.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Chun-Ting Chou, Chun-Wei Lu, Bing-Syuan Wu, Cheng-Che Tsai
Summary: This paper describes the study on the kinetic resolution of racemic secondary alcohols (O-nucleophiles) via stereoselective intramolecular allylic substitution. The reaction was achieved by the synergistic catalysis of palladium and chiral phosphoric acid, yielding chiral cis-1,3-disubstituted 1,3-dihydroisobenzofurans with a selective factor of up to 60.9 and a diastereomeric ratio of up to 7.8:1. The application of this methodology in the asymmetric synthesis of a compound with antihistaminic activity was demonstrated.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Pulluparambil Xavier Thresia Rinu, Sankaran Radhika, Gopinathan Anilkumar
Summary: The Julia-Kocienski (J-K) olefination is a modified version of Julia-Lythgoe olefination, widely used in the synthesis of E-alkenes for natural product synthesis. It has shown efficient protocols and recent developments in this area, providing a key step in the synthesis of various natural products.
Article
Chemistry, Organic
Zhen-Bang Chen, Ru-Xin Liu, Zi-Hao Li, Tong-Mei Ding, He-Yuan Bai, Zengming Shen, Shu-Yu Zhang
Summary: An efficient palladium-catalyzed enantioselective direct N-alkylation reaction using a novel axially chiral styrene-phosphine ligand SJTU-PHOS-1 was developed. The reaction showed good functional group compatibility and a wide range of substrate scope under mild conditions. Furthermore, DFT calculations revealed the coordination mode of the metal catalyst and the axially chiral styrene-phosphine ligand in enantioselectivity control.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Haigen Fu, Tianzhang Qi, Jose M. Carceller, Samantha N. MacMillan, Todd K. Hyster
Summary: In this study, a highly selective and stereoselective alkylation reaction of nitroalkanes was reported, catalyzed by an engineered flavin-dependent ene-reductase. This enzyme allows for the synthesis of tertiary nitroalkanes with high yield and enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Saikat Das, Qiupeng Hu, Azusa Kondoh, Masahiro Terada
Summary: Enantioselective protonation of diarylphosphine oxides with 2-vinyl azaheterocycle N-oxide derivatives was achieved using chiral bis(guanidino)iminophosphorane as the catalyst, where a chiral weak conjugate acid played a crucial role as the proton source. This method allows for a broadening of enantioselective reaction systems by utilizing less acidic pronucleophiles, and enables the synthesis of chiral metal complex ligands through reduction of phosphine oxide and N-oxide units.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Gonglin Li, Yan Zhang, Hongkun Zeng, Xiaoming Feng, Zhishan Su, Lili Lin
Summary: In this study, a novel asymmetric catalytic reaction was reported, in which the diastereoselectivity of the substrates was controlled by using a bispidine-based chiral amine catalyst and water. The resulting products showed potential anti-HIV-1 activity, with high yields and ee values. Control experiments and theoretical calculations revealed the diastereodivergent mechanism of the reaction, providing inspiration for further studies on diastereodivergent asymmetric synthesis.
Article
Chemistry, Organic
Jixin Pian, Qingqing Chen, Yujiao Luo, Zhifei Zhao, Jichang Liu, Lin He, Shi-Wu Li
Summary: An enantioselective cyclopropanation reaction of sulfoxonium ylides with beta,gamma-unsaturated ketoesters catalyzed by a chiral rhodium catalyst has been achieved, leading to the synthesis of various optically pure cyclopropanes.
Article
Chemistry, Organic
Babar Hussain Shah, Sardaraz Khan, Can Zhao, Yong Jian Zhang
Summary: An efficient method for the synthesis of 2,3-dihydrofurans with a quaternary stereocenter has been developed through Pd-catalyzed asymmetric allylic cycloaddition and a retro-Dieckmann fragmentation cascade. The one-pot process involves the allylic cycloaddition of vinylethylene carbonates with 3-cyanochromone and subsequent base-assisted retro-Dieckmann fragmentation, leading to chiral 3,4-disubstituted 2,3-dihydrofurans with high yields and excellent enantioselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xian-Liang Wang, Xing-Hao Yin, Jun-Zhao Xiao, Xue-Shun Jia, Liang Yin
Summary: A general synthesis of chiral 1,3-disubstituted allylsilanes was achieved through copper(I)-catalyzed asymmetric 1,4-conjugate silylation and subsequent Julia-Kocienski olefination. The prepared chiral compounds showed promising potential in asymmetric allylation reactions, with interesting match and mismatch phenomenon observed in the reaction of chiral aldehydes.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Dharma Theja Nannapaneni, Kiran Chinthapally, Ishita Hatial, Brandon L. Ashfeld, Brian S. J. Blagg
Summary: An efficient seven-step procedure for the synthesis of (25R)-cholesta-5,7-diene-36,26-diol from commercially available ergosterol in a yield of 25% is described. The synthesis involves Julia-Kocienski olefination of the aldehyde with benzothiazole sulfone ester in the presence of LiHMDS followed by reduction of the alkene. This research provides important insights and potential applications.
TETRAHEDRON LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Tsubasa Nakashima, Haruka Fujimori, Kohsuke Ohmatsu, Takashi Ooi
Summary: Intermediary radical cations, generated through single-electron oxidation of enol silyl ethers by excited Ir-based photocatalysts, are exploited as Bronsted acids for activating heteroarylcyanides. This enables the direct allylic C-H heteroarylation of enol silyl ethers under visible-light irradiation.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Kohsuke Ohmatsu, Yusuke Morita, Mari Kiyokawa, Takashi Ooi
Summary: The stereoselective cyanoalkylation of electron-deficient olefins with potassium cyanide and alkyl halides was developed using modular chiral 1,2,3-triazolium salts as catalysts with hydrogen bond-donor ability. The reaction involves enantioselective conjugate addition of a cyanide ion and consecutive diastereoselective alkylation of intermediary chiral triazolium enolates controlled by the catalyst. Properly tuned chiral triazolium ion as a catalyst and the presence of cyano functionality in the enolate are crucial for achieving high levels of acyclic stereocontrol.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Kohsuke Kato, Daisuke Uraguchi, Takashi Ooi
Summary: A new o-QM catalyst was developed for the dehydridative oxidation of benzylic alcohols. The introduction of an overcrowded olefinic component into o-QM induced structural distortion, beneficial for imparting triarylmethylium character and regenerability. The zwitterionic resonance form of o-QM generated through photoexcitation and relaxation exhibited dehydridation activity.
Article
Chemistry, Multidisciplinary
Kohsuke Ohmatsu, Haruka Fujimori, Kodai Minami, Kosuke Nomura, Mari Kiyokawa, Takashi Ooi
Summary: Thioamidate ions are introduced as competent cocatalysts for multisite proton-coupled electron transfer catalysis. The high pK(a) values of their conjugate acids contribute to the effectiveness of these anions. The combined use of stable tetrabutylammonium thioamidate and an appropriate Ir-based photosensitizer enables the C-H alkylation of various C-H donors, including simple cyclic alkanes, under visible-light irradiation.
Article
Chemistry, Physical
Kodai Minami, Kohsuke Ohmatsu, Takashi Ooi
Summary: An unconventional cooperative catalysis for hydrogen-atom-transfer-mediated acceptorless dehydrogenative cross-coupling is described in this study. By using specific catalysts, C-H/C-H cross-couplings between heteroatom-containing C-H donors and enamides or 1,1-diarylethenes were achieved under visible-light irradiation without the need for oxidants, hydrogen evolution catalysts, or electrodes. The key to this catalysis is the susceptibility of the conjugate acid of the triazolium amidate, amide triazolium, to single-electron reduction to complete the catalytic cycle.
Article
Chemistry, Organic
Kohsuke Ohmatsu, Yusuke Morita, Mari Kiyokawa, Kimihiro Hoshino, Takashi Ooi
Summary: A catalytic asymmetric Strecker reaction of ketoimines with potassium cyanide (KCN) has been developed, utilizing a chiral 1,2,3-triazolium ion as a catalyst in combination with a protic additive. Control experiments revealed the involvement of a retro-Strecker reaction, leading to decreased product yield and enantioselectivity. This approach allows for highly efficient and enantioselective cyanide addition to various ketoimines.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Organic
Daisuke Uraguchi, Takashi Ooi
Summary: The study demonstrates the control of multiple selectivity using P-spiro chiral tetraaminophosphonium ion, including enantioselectivity, geometry, regiochemistry, diastereomer formation, and reaction pathway. Theoretical investigation reveals key elements for achieving multiple selectivity control.
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN
(2021)
Article
Chemistry, Multidisciplinary
Hong Yi, Kimberly M. Osten, Tetyana Levchenko, Alex J. Veinot, Yoshitaka Aramaki, Takashi Ooi, Masakazu Nambo, Cathleen M. Crudden
Summary: A series of chiral Au-13 nanoclusters were successfully synthesized and characterized, exhibiting high luminescence and stability. This opens up opportunities for further investigation into the impact of chirality on the properties of these clusters.
Article
Chemistry, Multidisciplinary
Daisuke Uraguchi, Kohsuke Kato, Takashi Ooi
Summary: An o-quinone methide (o-QM) with an overcrowded olefinic framework is introduced, showing dehydridation activity due to its enhanced zwitterionic character, especially under photoexcitation. Experimental analysis and density functional theory calculations provide mechanistic insights, revealing that the o-QM operates in dehydridative catalysis for the oxidation of benzylic secondary alcohols.
Article
Chemistry, Organic
Yuto Kimura, Daisuke Uraguchi, Takashi Ooi
Summary: The protocol described enables a highly stereoselective [3 + 2]-cycloaddition of cyclopropylurea with alpha-substituted acrylates, leading to the efficient synthesis of a variety of stereochemically defined 5-membered alicyclic alpha-quaternary beta-amino acids, which are useful building blocks for beta-peptides and peptidomimetics.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Tsubasa Nakashima, Kohsuke Ohmatsu, Takashi Ooi
Summary: The collaboration between an Ir-based photosensitizer with mild oxidizing ability and a thiol catalyst enables efficient allylic C-H functionalization of enol silyl ethers with imines under visible light irradiation. Subsequent transformations of the aminoalkylated enol silyl ethers allow for the facile construction of unique molecular frameworks such as functionalized octahydroisoindol-4-one.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
