Article
Chemistry, Organic
Nan-Fang Mo, Ying Zhang, Zheng-Hui Guan
Summary: An asymmetric organocatalyzed three-component Povarov reaction has been developed to construct azaspirocycles. A chiral phosphoric acid catalyst with a unique structure was highly efficient in the reaction, leading to a wide range of azaspirocycles in high yields and excellent enantioselectivities. This reaction has expanded the scope of the traditional Povarov reaction.
Article
Chemistry, Multidisciplinary
Jie Ouyang, Rajat Maji, Markus Leutzsch, Benjamin Mitschke, Benjamin List
Summary: Here, we report the design of a highly enantioselective, catalytic (4 + 3) cycloaddition reaction enabled by strong and confined IDPi Lewis acids. This reaction allows the synthesis of novel compounds with multiple stereocenters from gem-dialkyl 2-indolylalcohols and dienolsilanes. The method exhibits broad substrate scope and versatile downstream chemical modifications. Density functional theory-supported mechanistic studies reveal the significance of the in-situ generated silylium species in an overall concerted yet asynchronous cycloaddition.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Stefano Nejrotti, Francesco Marra, Emanuele Priola, Andrea Maranzana, Cristina Prandi
Summary: The reactivity of furan-ynes in combination with pyridine and quinoline N-oxides in the presence of a Au(I) catalyst has been studied, enabling the synthesis of three different heterocyclic scaffolds. Selective access to two out of the three possible products has been achieved through the fine-tuning of the reaction conditions. The reactions proceed smoothly at room temperature and open-air, and were further extended to a broad substrate scope, affording functionalized dihydropyridinones and pyranones.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Masao Ohashi, Dan Tan, Jiayan Lu, Cooper S. Jamieson, Daiki Kanayama, Jiahai Zhou, K. N. Houk, Yi Tang
Summary: The synthesis of cis-decalin structures using [4 + 2] cycloaddition with high stereoselectivity is challenging. In this study, we investigated the biosynthetic pathway of the fungal natural product fischerin (1) and identified a novel pericyclase, FinI, which catalyzes this reaction. The cocrystal structure of FinI, a predicted O-methyltransferase, with the product and SAM provides valuable insights into the natural formation of cis-decalin.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yuan-He Li, Su-Lei Zhang, Yong Lu, Bo Xiao, Tian-Yu Sun, Qian-Qian Xu, Jia-Hua Chen, Zhen Yang
Summary: A highly enantioselective catalytic system for exo-Diels-Alder reactions was developed using bispyrrolidine diboronates(BPDB). Activated by various Lewis or Bronsted acids, BPDB can catalyze highly stereoselective asymmetric exo-Diels-Alder reactions. The catalyst can also distinguish between different binding sites to achieve highly regioselective reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Julia O. Strelnikova, Alexander N. Koronatov, Nikolai Rostovskii, Alexander F. Khlebnikov, Olesya Khoroshilova, Mariya A. Kryukova, Mikhail S. Novikov
Summary: The domino reaction catalyzed by Rh-2(Piv)(4) leads to the formation of N-sulfonylated (Z)-2-(2-aminovinyl)imidazoles, providing a direct and flexible access to the desired compounds.
Article
Chemistry, Organic
Depeng Duan, Huixin Qiu, Mengdie Tang, Ran Song, Wen Si, Daoshan Yang, Jian Lv
Summary: This study reports a [4+2] cycloaddition catalyzed by Lewis acid HfCl4, leading to high yields of polysubstituted 4H-pyrans. The reaction conditions are mild and exhibit excellent selectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Po Yuan, Christa K. G. Gerlinger, Jan Herberger, Tanja Gaich
Summary: The first asymmetric synthesis of pepluanol A was achieved using a concise route with a stereoconvergent intramolecular Diels-Alder reaction. The key step involved a Nozaki-Hiyama-Kishi reaction to connect the enone system and diene, followed by a stereoconvergent IMDA reaction to furnish the natural product carboskeleton in 7 steps. The reactions were carried out successfully on a gram scale up to an advanced intermediate, including the stereoconvergent intramolecular Diels-Alder reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Daniel P. Schwinger, Thomas Pickl, Thorsten Bach
Summary: Cyclohept-1-ene-1-carbaldehyde undergoes photoinduced E & RARR; Z isomerization at & lambda; =350 nm. The ring strain facilitates various reactions, including Diels-Alder cycloadditions, [3 + 2] cycloadditions, and enereactions. The products obtained are trans-fusedat the cycloheptane core and yield up to 82%. Single crystal X-ray analyses confirm the structure and relative configuration. In the presence of BF3 and 2,3-dimethylbuta-1,3-diene, cyclohept-1-ene-1-carbaldehyde undergoes a stereoselective rearrangement to form a tricyclic ketone (87%).
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Yan Jiang, Hao-Jie Ma, Xue-Long Wang, Yi Yang
Summary: A Yb(OTf)(3)-catalyzed formal (4 + 3) cycloaddition reaction was successfully achieved using donor-acceptor cyclopropanes and 3-benzylideneindoline-2-thiones as reactants. Functionalized 5,10-dihydro-2H-thiepino[2,3-b]indole derivatives were synthesized with good yields and moderate to good diastereoselectivity. This reaction represents the first (4 + 3) cycloaddition of 3-benzylideneindoline-2-thiones.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Organic
Rui Wu, Dong Zhu, Shifa Zhu
Summary: This review showcases the advances in dirhodium-catalyzed transformations, including cycloisomerization, hetero-Diels-Alder reactions, ene reactions, arylation, radical oxidation reactions, and C-H activation. In these reactions, dirhodiums can serve as not only redox-neutral catalysts but also redox catalysts.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Lei Yu, Wenhai Li, Anyawan Tapdara, Sara Helen Kyne, Mandeep Harode, Rasool Babaahmadi, Alireza Ariafard, Philip Wai Hong Chan
Summary: An efficient chiral gold(I) complex-catalyzed synthetic method for the regio- and enantioselective nitroso-Diels-Alder (NDA) reaction of 1,6-diyne esters with nitrosobenzenes is described. The reaction provides access to a wide range of 3,5,6,8a-tetrahydro-1H-benzo[c][1,2]oxazines as a single regioisomer with high yields and enantiomeric excess values.
Article
Chemistry, Multidisciplinary
Debsena Chakraborty, Shamsad Ali, Pritam Choudhury, Neal Hickey, Partha Sarathi Mukherjee
Summary: Chemical reactions inside enzyme-mimicking hosts, such as cages and macrocycles, have been the focus of research. This study demonstrates how the shape of the molecular container influences the divergent synthesis of nonisomeric products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Rebecca L. Spicer, Helen M. O'Connor, Yael Ben-Tal, Hang Zhou, Patrick J. Boaler, Fraser C. Milne, Euan K. Brechin, Guy. C. Lloyd-Jones, Paul J. Lusby
Summary: Coordination cage catalysis is a strategy that utilizes a cage as an exogenous catalyst, rather than relying on the endogenous binding of substrates. The cage alters the properties of a cofactor guest, which then transfers reactivity to the bulk-phase to catalyze reactions.
Article
Chemistry, Organic
Gary L. Points, Christopher M. Beaudry
Summary: Substituted carbazoles are efficiently synthesized from 3-triflato-2-pyrones and alkynyl anilines, allowing for multiple substituents with complete control of regiochemistry, resulting in complex substitution patterns. This strategy can also be applied to prepare substituted bicarbazoles and related biaryls, and has been demonstrated in the synthesis of the carbazole natural product clausine C.
Article
Chemistry, Organic
Zheng-Fei Li, Yun Yao, Yan-Jun Xu, Chong-Dao Lu
JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Organic
Chun-Tian Li, Hui Liu, Yun Yao, Chong-Dao Lu
Article
Chemistry, Organic
Jie Feng, Hui Liu, Yun Yao, Chong-Dao Lu
Summary: A series of alpha-mercapto-beta-amino acid derivatives were successfully synthesized through azaenolization of alpha-sulfanyl N-tert-butanesulfinylimidates and their nucleophilic addition to N-tosyl imines via a Mannich-type reaction. The resulting derivatives bearing a beta-sulfonylamino sulfide moiety participated in various inter- and intramolecular transformations.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Correction
Chemistry, Organic
Jie Feng, Hui Liu, Yun Yao, Chong-Dao Lu
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Nuermaimaiti Yisimayili, Hui Liu, Yun Yao, Chong-Dao Lu
Summary: Vicinal quaternary-tertiary carbon stereocenters were constructed with excellent stereoselectivity through aza-enolization and conjugate addition, showcasing a successful acyclic stereocontrol strategy. The facile stereodivergent synthesis of all four diastereomers of the Michael-type alkylation adducts was achieved by manipulating the absolute configuration of the sulfinyl group and/or the alpha-stereocenter in the ketimine.
Article
Chemistry, Organic
Nuermaimaiti Yisimayili, Hui Liu, Yun Yao, Chong-Dao Lu
Summary: In this study, alpha-tertiary hydroxyimines were stereoselectively synthesized from enantioenriched N-tert-butanesulfinyl ketimines using potassium tertbutoxide, molecular oxygen, and trimethyl phosphite. The stereoselective hydroxylation of acyclic ketimines with two sterically similar alpha-substituents was achieved by controlling the geometry of the metalloenamine intermediates and the facial selectivity of hydroxylation, demonstrating the synthetic utility through successful diastereoselective synthesis of highly substituted beta-amino alcohols.
Article
Chemistry, Organic
Jie Feng, Hui Liu, Yun Yao, Chong-Dao Lu
Summary: The first synthesis of primary tert-butanesulfonimides with high enantiopurity was achieved by imination of enantioenriched N'-tert-butanesulfinyl amidines, followed by hydrazinolysis. N'-Sulfinyl amidines served as imination precursors during copper-catalyzed sulfonyl nitrene transfer or iodonitrene-based NH transfer. Further transformations allowed the introduction of diverse substituents on the nitrogen of S=N.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Zheng-Fei Li, Chong-Lin Zhu, Yun Zhang, Yun Yao, Chong-Dao Lu
Summary: A new Mannich reaction was developed to prepare 3-amino-3-substituted oxindoles containing a specific chiral carbon. Excellent stereocontrol was achieved through deprotonation and C-C bond formation, allowing for the construction of contiguous quaternary and tetrasubstituted stereocenters with high stereo-selectivity.
Article
Chemistry, Organic
Nuermaimaiti Yisimayili, Li-Feng Chu, Jie Feng, Chong-Dao Lu
Summary: N-Sulfinyl metalloenamines, generated by deprotonating alpha-linear N-tert-butariesulfinyl ketimines, reacted with nitroalkenes via stereoselective conjugate addition to give Michael adducts with opposite stereochemistry. In the presence of excess base, the adducts derived from alpha-linear ketimines were further stereoselectively deprotonated to afford N-sulfinyl (Z)-enamine derivatives with good yields and stereoselectivities. A reaction model was proposed to rationalize the observed stereochemistry.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Tao Liu, Yun Yao, Nuermaimaiti Yisimayili, Chong-Dao Lu
Summary: In this study, a method for the hydroxymethylation of alpha-branched ketimines using formaldehyde equivalents was developed, allowing for the stereoselective construction of acyclic quaternary stereocenters bearing two similar substituents.
Article
Chemistry, Organic
Li-Feng Chu, Yun Yao, Chong-Dao Lu
Summary: A protocol was developed to achieve stereoselective alpha-alkynylation of alpha,alpha-disubstituted N-tert-butanesulfinyl ketimines using a specific reagent in the presence of fluoride. This method allows the construction of less accessible acyclic quaternary stereocenters.
Article
Chemistry, Organic
Chong-Lin Zhu, Yun Yao, Chong-Dao Lu
Summary: A single-flask cascade reaction method was developed for the stereoselective alpha-allylic alkylation of alpha-branched N-tert-butanesulfinyl ketimines, allowing the construction of acyclic quaternary stereocenters bearing two sterically and electronically similar substituents.
Article
Chemistry, Multidisciplinary
Ranran Li, Bin Ma, Shengtao Li, Chongdao Lu, Peng An
Summary: This article describes a series of chalcogen-doped nanographenes and their oxides. The molecular design of these nanographenes is based on the insertion of different chalcogens into the hexa-peri-hexabenzocoronene backbone. The nonplanar conformations of these nanographenes, except for the oxygen-doped one, exhibit better solubility compared to the planar hexa-peri-hexabenzocoronene. Single-crystal X-ray diffractometry confirms the three-dimensional structures of these nanographenes. The photophysical properties of each structure, including UV-vis absorption, fluorescence, chiroptical, charge distribution, and orbital gaps, are investigated experimentally or theoretically. The properties are significantly influenced by the doped chalcogen and its oxidative state. It is noteworthy that the selenium-doped nanographene or its oxide undergoes a selenium extrusion reaction to form hexa-peri-hexabenzocoronene quantitatively upon heating or adding an acid, which can be considered as precursors of hydrocarbon hexa-peri-hexabenzocoronene.
Article
Chemistry, Multidisciplinary
Qian-Yi Wang, Teng-Fei Liu, Li-Feng Chu, Yun Yao, Chong-Dao Lu
Summary: In the presence of a chiral spiro phosphoric acid catalyst, the asymmetric reaction of disubstituted ketenes with N-H pyrroles occurred to afford enantioenriched C-acylated pyrroles bearing alpha-stereogenic carbon centres. This reaction represents a rare example of catalytic asymmetric reaction of ketenes with carbon-based nucleophiles, with significant research implications.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Fan Tang, Peng-Ju Ma, Yun Yao, Yan-Jun Xu, Chong-Dao Lu
CHEMICAL COMMUNICATIONS
(2019)
