Article
Chemistry, Multidisciplinary
Xin He, Pengchen Ma, Yuhai Tang, Jing Li, Shenyu Shen, Martin J. Lear, K. N. Houk, Silong Xu
Summary: We report a phosphine-catalyzed (3 + 2) annulation of cyclopropenones with various electrophilic pi systems, yielding products including butenolides, butyrolactams, maleimides, and iminomaleimides in high yields with a wide range of substrates. An alpha-ketenyl phosphorous ylide is identified as the key intermediate, which undergoes preferential catalytic cyclization with aldehydes. This phosphine-catalyzed activation of cyclopropenones provides a versatile C-3 synthon for formal cycloadditon reactions.
Article
Chemistry, Organic
Zhan-Cai Ma, Lin-Wen Wei, Yuan Huang
Summary: We have developed a highly efficient stereodivergent [4 + 2] annulation reaction using palladium catalysis to synthesize N-heterocycles with 1,3-nonadjacent stereogenic centers. The diastereoselectivity of the reaction is dependent on the polarity of solvents used. Additionally, good enantioselectivities were achieved by employing the chiral ligand Wingphos.
Article
Chemistry, Multidisciplinary
Fuhao Zhang, Xuan Dai, Lei Dai, Wenrui Zheng, Wai-Lun Chan, Xiaodong Tang, Xumu Zhang, Yixin Lu
Summary: A phosphine-catalyzed highly enantioselective and diastereoselective (3+2) annulation reaction has been developed, allowing convenient access to a range of highly functionalized chiral pyrrolidines. This method utilizes vinylcyclopropanes as a synthon for phosphine-mediated asymmetric annulation, offering new opportunities for the application of cyclopropanes substrates in phosphine-catalyzed organic transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Chunjie Ni, Shiyu Pan, Chen Yuan, Shuya Qin
Summary: Amine-catalyzed [3 + 3] annulations of β-acetoxyallenoates with 1C,3N-bisnucleophiles have been successfully established, providing a convenient and efficient method to synthesize novel 1,2-fused benzimidazole derivatives in moderate to good yields. Preliminary attempts on the asymmetric version of this reaction using cinchona alkaloid-based tertiary amines have also been explored.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Baixue Liu, Peng Liu, Xue Wang, Feng Feng, Zhen Wang, Wenqiang Yang
Summary: A general method for the gram-scale enantioselective synthesis of P-stereogenic cyclic phosphine oxides has been developed using copper-catalyzed dynamic kinetic resolution, leading to high yields and high enantioselectivities. The resulting products can be easily reduced to obtain useful P(III)-stereogenic cyclic phosphines. A proposed mechanism involves the unusual rapid racemization of SPOs.
Article
Chemistry, Organic
Dongxin Zhang, Qihang Cheng, Lvjia Chen, Huiqing Deng, Hu Cai, Qian-Feng Zhang
Summary: Copper triflate-catalyzed annulations of oxindole based spirocyclic donor-acceptor cyclopropanes and ynamides have been developed for the synthesis of biologically important spirocyclopenteneoxindoles. These reactions tolerated a wide scope of substrates and provided the desired products in good to high yields with high diastereoselectivities under mild conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Atanu Mondal, Bishnupada Satpathi, S. S. Ramasastry
Summary: This study demonstrates a novel strategy for the phosphine-catalyzed intramolecular vinylogous aldol reaction of alpha-substituted enones, leading to the synthesis of various novel cyclic compounds and dibenzocycloheptanones with two contiguous stereocenters. The scope of this work is further expanded through transformations of the IVAR adducts, resulting in the synthesis of benzannulated nine-membered carbocyclic systems, interesting classes of dienes, trienes, and dienynes, as well as analogs of echinolactone D and russujaponol F.
Article
Chemistry, Organic
Junfeng Fu, Ingrid Rakielle Tsapy Takia, Peng Chen, Wei Liu, Chengjun Jiang, Weijun Yao, Xiaofei Zeng, Yongjiang Wang, Xiaoyu Han
Summary: The phosphine-mediated tandem [3 + 2] cyclization/intramolecular Wittig reaction of 3-aroylcoumarin with alkynone allows the synthesis of 2-chromanone-fused bicyclo[3.2.0]heptenones in moderate to high yields with remarkably high regio- and diastereoselectivities under mild reaction conditions, providing an extremely simple, economical, and straightforward synthetic method for constructing complex cyclic building blocks with potential biological applications.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Xinghua Wang, Shi-Jun Li, Ya-Nan Wang, Donghui Wei, Yu Lan
Summary: Desymmetrizing reactions of olefins catalyzed by N-Heterocyclic carbene (NHC) have been rapidly developing, but the origins of the chemo- and stereoselectivities in these reactions are still poorly understood. This study proposes a mechanistic map to predict how these selectivities are controlled by different active intermediates and contradicts a previous proposition regarding the determination of product structures by a transformation between a pair of isomers.
Article
Chemistry, Multidisciplinary
Kuan Li, Sen Yang, Bing Zheng, Wei Wang, Yongjun Wu, Jing Li, Hongchao Guo
Summary: In this study, a new type of delta-vinylvalerolactone was designed and synthesized as a precursor in Pd-catalyzed [6+3] cycloaddition. The reaction resulted in nine-membered 1,2-dinitrogen-containing heterocycles in high yields with excellent diastereoselectivity. Further transformation of these ring-fused products led to the formation of unusual tetracyclic bridged-ring compounds without loss of diastereoselectivity.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Ahmad A. Ibrahim, Pei-Hsun Wei, Gero D. Harzmann, Divya Nalla, Mukulesh Mondal, Kraig A. Wheeler, Nessan J. Kerrigan
Summary: This article discusses the full details of optimization studies of the phosphine-catalyzed ketene homodimerization reaction and the development of an asymmetric variant. It also reveals studies towards the development of a phosphine-catalyzed ketene heterodimerization reaction, and includes a discussion of possible reaction mechanisms supported by spectroscopic analysis of intermediates and trapping experiments.
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, Organic
Bai Shi, Fangyi Jin, Qi Lv, Xinrong Zhou, Zhixiao Liao, Chenxia Yu, Kai Zhang, Changsheng Yao
Summary: A N-heterocyclic carbene (NHC) catalyzed formal [3 + 3] annulation reaction between & delta;-acetoxy allenoates and 1C,3O-bisnucleophiles has been developed for the synthesis of highly functionalized 4H-(fused)pyrans, with a broad substrate scope (30 examples, up to 77% yield).
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Chun -Lin Zhang, Hai-Ying Wang, Ying Huang, Xin-Han Wang, Song Ye
Summary: An N-heterocyclic carbene-catalyzed three-component reaction has been developed for the synthesis of multisubstituted benzenes. The reaction demonstrates mild conditions, high efficiency, and chemoselectivity, leading to the formation of pentasubstituted benzenes in good to high yields.
Article
Chemistry, Organic
Qi Yin, Xiaolu Wen, Yiwei Chen, Xiangnan Gong, Lin Hu
Summary: The efficient catalytic asymmetric [4 + 1] reaction developed in this study enables the synthesis of functionalized organic compounds with consecutive quaternary and tertiary carbon stereocenters in high diastereoselectivities and enantioselectivities. The products obtained can be readily transformed into chiral compounds through debenzoylation and alkylation reactions, providing a versatile platform for further chemical transformations.
Article
Chemistry, Multidisciplinary
Byungjun Kim, Yongjae Kim, Sarah Yunmi Lee
Summary: A stereodivergent method for the Michael addition of aryl acetic acid esters to alpha,beta-unsaturated aldehydes has been developed using a combination of a chiral pyrrolidine and a chiral Lewis base as catalysts. The reaction allows for the synthesis of products with high enantio- and diastereoselectivity, which can be further transformed into a variety of valuable enantioenriched structures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Adrian Tlahuext-Aca, Sarah Yunmi Lee, Shu Sakamoto, John F. Hartwig
Summary: A new method for the direct catalytic arylation of simple arenes using aryl bromides is described. The method does not rely on directing groups and instead utilizes a synergistic catalytic cycle involving phosphine-ligated silver complexes and palladium catalysts. Mechanistic experiments indicate that cleavage of the C-H bond by silver is the rate-determining step in the catalytic cycle.
Article
Nanoscience & Nanotechnology
Sangwon Lee, Baekjun Kim, Hyun Cho, Hooseung Lee, Sarah Yunmi Lee, Eun Seon Cho, Jihan Kim
Summary: The study utilizes machine learning and evolutionary algorithms to identify metal-organic frameworks with desired properties.
The results demonstrate that the algorithm discovered multiple MOFs with methane working capacity surpassing the world record.
This methodology can be extended to other important applications.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Organic
Sudeep Sarkar, Natalia Wojciechowska, Adam A. Rajkiewicz, Marcin Kalek
Summary: A metal-free arylation reaction using diaryliodonium salts and thiols has been developed. The C-S bond formation is achieved under mild and experimentally simple conditions with the application of a strong organic base. This method allows for the synthesis of aryl sulfides containing a broad range of aryl groups from various thiols including aryl, heteroaryl, and alkyl thiols. The mechanism of the reaction was studied and determined to proceed via an inner sphere pathway involving the formation of an Ar2I(SR) intermediate, followed by reductive elimination.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Justyna Golebiewska, Agnieszka Bartoszewicz, Marcin Kalek, Jacek Stawinski
Summary: The study aims to explore the possibility of further functionalizing the sulfur or selenium heteroatoms in nucleotide analogues to create a second generation with new biological properties.
PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS
(2022)
Article
Chemistry, Organic
Byungjun Kim, Yongjae Kim, Sarah Yunmi Lee
Article
Chemistry, Physical
Soojin Kwak, Jeongin Choi, Jimin Han, Sarah Yunmi Lee
Summary: This study presents a Lewis pair-catalyzed process for the selective addition of secondary phosphine oxides to allenoates. Mechanistic studies reveal that the deprotonation of a P-H bond of a SPO by a phosphonium zwitterion is the rate-determining step in the reaction. The reaction proceeds through a catalytic cycle to form alkenylphosphorus building blocks.
Article
Chemistry, Physical
Margot Jacquet, Silvio Osella, Ersan Harputlu, Barbara Palys, Monika Kaczmarek, Ewa K. Nawrocka, Adam A. Rajkiewicz, Marcin Kalek, Pawel P. Michalowski, Bartosz Trzaskowski, C. Gokhan Unlu, Wojciech Lisowski, Marcin Pisarek, Krzysztof Kazimierczuk, Kasim Ocakoglu, Agnieszka Wieckowska, Joanna Kargul
Summary: The covalent attachment of metalorganic wires on electron-rich surfaces, fluorine-doped tin oxide and single-layer graphene, leads to the promotion of p-doping of the graphene and significantly enhanced photocurrent, demonstrating potential applications in various fields.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Applied
Abhishek Pareek, Marcin Kalek
Summary: The Morita-Baylis-Hillman reaction utilizing N-alkylquinolinium salts as electrophiles has been developed. The reaction is catalyzed by DBU and involves regioselective dearomatization at the C-2 position, yielding a wide range of alpha-(1,2-dihydroquinolin-2-yl)vinyl esters, ketones, and sulfones. The scope of the reaction has been extended to N-alkylpyridinium salts, which require moderately electron-withdrawing substituents to achieve good reactivity.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Sudeep Sarkar, Marcin Kalek
Summary: We have developed a metal-free method for the direct S-arylation of phosphorothioate diesters using diaryliodonium salts. This allows for the preparation of a wide range of S-aryl phosphorothioates, including complex molecules, as well as other arylated organophosphorus compounds. The reaction proceeds with retention of stereochemistry at the phosphorus atom, providing convenient access to P-chiral products. The mechanism of the reaction has been elucidated using DFT calculations.
Article
Chemistry, Organic
Natalia Wojciechowska, Krzysztof Bienkowski, Renata Solarska, Marcin Kalek
Summary: Compared to chiral iodoarenes in organocatalysis, stoichiometric oxidants can be replaced by electric stimuli in electrosynthesis. By screening reaction parameters, an enantioselective electrochemical oxidation mediated by a chiral iodoarene has been achieved for the first time. However, the efficiency is relatively low due to the difficult electrochemical oxidation of the applied iodoarene catalyst.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Somayyeh Sarvi Beigbaghlou, Robert S. Yafele, Marcin Kalek
Summary: An electrochemical method for the oxidation of naphthols and phenols with intramolecular C-O bond formation has been developed. Optimization of reaction conditions allowed for the use of free phenols as starting materials instead of aryl methyl ether substrates. The reaction produces spirolactones and spiroethers in high yields up to 97% under simple experimental conditions without the need for catalysts or stoichiometric oxidants, and only hydrogen is generated as a byproduct.
SYNTHESIS-STUTTGART
(2023)
Article
Biochemistry & Molecular Biology
Mateusz Jedrzejewski, Barbara Belza, Iwona Lewandowska, Marta Sadlej, Agata P. Perlinska, Rafal Augustyniak, Thomas Christian, Ya-Ming Hou, Marcin Kalek, Joanna I. Sulkowska
Summary: The Nep1 protein plays a crucial role in the formation of small ribosomal subunits in eukaryotes and archaea, and it is responsible for the methylation of pseudouridine during pre-rRNA processing. Through a combination of bioinformatics, computational, and experimental methods, this study investigates the deprotonation of pseudouridine in the Nep1 active site by a distant aspartate residue. It identifies a potential proton-transfer mediator and confirms that both an amino acid and a water molecule can facilitate proton transfer, with the water-mediated pathway being the most favorable.
COMPUTATIONAL AND STRUCTURAL BIOTECHNOLOGY JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Serim Choi, Yongseok Choi, Yongjae Kim, Jaehoo Lee, Sarah Yunmi Lee
Summary: Copper-catalyzed synthesis of quaternary carbon centers through C(sp(3))-C(sp(2)) bond-forming reaction between tertiary alkyl halides and arene rings of aniline derivatives is enabled by the use of bidentate bis(cyclopropenimine) ligands. The copper catalyst, bound by imino-nitrogen atoms of these ligands, effectively activates tertiary halides to generate alkyl radicals and allows them to react with aryl nucleophiles under mild conditions with short reaction times. Various tertiary halides bearing carbonyl functional groups can be coupled with secondary or primary anilines to furnish quaternary carbon centers in good yields. Several mechanistic observations support the proposed catalytic cycle.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Byungjun Kim, Yuna Song, Sarah Yunmi Lee
Summary: In this study, a silver-catalyzed method was developed for the enantio- and diastereodivergent synthesis of chiral pyroglutamic acid esters with multiple stereocenters. By utilizing catalyst control and stereospecificity, all four product stereoisomers containing two adjacent stereocenters can be accessed with high stereoselectivity.
CHEMICAL COMMUNICATIONS
(2021)