Article
Chemistry, Multidisciplinary
Haoran Dong, Dachao Hu, Benke Hong, Jin Wang, Xiaoguang Lei
Summary: The first total syntheses of four natural antibiotics, vermisporin, PF1052/AB4015-A, AB4015-L, AB4015-B, and one hydrogenated natural product derivative, AB4015-A2, featuring a tetramic acid bearing cis-decalin ring, are reported. The functionalized cis-decalin ring was constructed via a diastereoselective intramolecular Diels-Alder (IMDA) reaction, with a rare endo-boat transition state. The efficient installation of the sterically hindered epoxy group in vermisporin, PF1052/AB4015-A, and AB4015-L was achieved through an intramolecular neighboring-group-oriented strategy, and the desired tetramic acid structure was obtained through a one-pot aminolysis/Dieckmann condensation cascade using L-amino acid derivatives. The total synthesis allowed for the unequivocal verification of the absolute configuration of these natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Marlene Fadel, Erick M. Carreira
Summary: The first total synthesis of (+)-pedrolide, a tigliane-derived diterpenoid featuring an unprecedented 5-5-6-6-3 carbon skeleton, was achieved. A key step in the synthesis involved the construction of the bicyclo[2.2.1]heptane core via an intramolecular cyclopentadiene-Diels-Alder cycloaddition. A norbornadiene was used as a surrogate for cyclopentadiene, and the unmasking of the cyclopentadiene was achieved through a complex Diels-Alder reaction cascade. This synthesis also provided a novel approach to a densely functionalized carane in an efficient and enantioselective manner.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Po Yuan, Tanja Gaich
Summary: In this study, we reported a synthetic method for the enantioselective and convergent total synthesis of (+)-pepluanol A, a natural product with a structurally intriguing skeleton. The method achieved high diastereoselectivity and convergency through key reactions for constructing the unique framework.
Article
Chemistry, Multidisciplinary
Bo Qin, Zhepei Lu, Yanxing Jia
Summary: We have successfully achieved the divergent total synthesis of four kopsane alkaloids, which share a complex heptacyclic caged ring system. Key transformations in this synthesis include an asymmetric Diels-Alder reaction for constructing the central bicyclo[2.2.2]octane moiety and the quaternary stereocenter at C20, a SmI2-mediated cascade reduction/aldol reaction for constructing the five-membered ring and the quaternary stereocenter at C7, and a late-stage cascade reductive amination/cyclization for establishing the highly strained caged ring system.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Shaolei Ding, Yingbo Shi, Baochao Yang, Min Hou, Haibing He, Shuanhu Gao
Summary: We describe the asymmetric total synthesis of periglaucines A-C, N,O-dimethyloxostephine and oxostephabenine. Key strategies include a regio- and diastereoselective Hayashi-Miyaura reaction, an intramolecular photoenolization/Diels-Alder reaction, and a bio-inspired intramolecular Michael addition and transannular acetalization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Yu-Tao He, Li-Xuan Li, Xiaohong Lin, Bao-Long Hou, Chuang-Chuang Li
Summary: The rhodium-catalyzed bridged (3+2) cycloaddition cascade reactions of N-sulfonyl-1,2,3-triazoles described in this study efficiently allowed the construction of various functionalized bridged ring systems, including the highly strained polycyclic bicyclo[2.2.2]octa[b]indole core of fruticosine.
Article
Chemistry, Multidisciplinary
Johannes Gramueller, Philipp Dullinger, Dominik Horinek, Ruth M. Gschwind
Summary: This study elucidated the spatial structure and hydrogen bonding of BINOL derived chiral phosphoric acids (CPAs) and N-(ortho-hydroxyaryl) imines through experimental and computational methods. It experimentally validated the bidentate binding of catalyst and substrate via two hydrogen bonds. By adjusting steric repulsion and noncovalent interactions, rigid and well-defined CPA/imine monomers could be obtained. The structure of the complex, revealed by NOESY studies and theoretical calculations, pointed out the origin of the stereoselectivity for downstream transformations.
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, Multidisciplinary
Chengsen Cui, Mingji Dai
Summary: We present a highly efficient and convergent strategy for synthesizing UCS1025A and its diastereomer tetra-epi-UCS1025A. UCS1025A is a representative member of the naturally occurring pyrrolizidinone polyketides, some of which exhibit potent antibacterial, antifungal, and anticancer activities. Our approach involves a tandem carbonylative Stille cross coupling and Diels-Alder reaction to form a key C-C bond and construct the trans-decalin system. The process uses carbon monoxide as a linchpin to connect a vinyl triflate and a vinylstannane, resulting in the desired enone moiety for subsequent intramolecular Diels-Alder cyclization. Additionally, our synthesis provides a versatile method for synthesizing other pyrrolizidinone-containing polyketides.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Kenshu Fujiwara, Takaya Itagaki, Tetsuo Tokiwano
Summary: The total synthesis of selaginellin A isolated from Selaginella tamariscina was achieved through an eight-step process, and the study found that the addition of a trace amount of trifluoroacetic acid in NMR analysis can improve the reproducibility of its chemical shifts.
TETRAHEDRON LETTERS
(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, Organic
Pablo Wessig, Dominik Badetko, Lukas Wichterich, Eric Sperlich, Alexandra Kelling
Summary: The total syntheses of three arylnaphthalene lignans were developed using a regioselective intramolecular Photo-Dehydro-Diels-Alder (PDDA) reaction. The improvement of the photochemical step was achieved by triplet sensitization with xanthone. This work is a continuation of a previous publication about the total synthesis of lignans using the PDDA reaction.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(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
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)
Article
Chemistry, Multidisciplinary
Julian Baars, Isabelle Grimm, Dirk Blunk, Joerg-Martin Neudoerfl, Hans-Guenther Schmalz
Summary: A 12-step total synthesis of the natural product dysiherbol A was achieved, revealing the need for revision of the originally proposed structure and absolute configuration. The synthesis involved key steps including Cu-catalyzed addition/enolate-trapping, Au-catalyzed double cyclization, and late installation of the C5-bridgehead methyl group. Spectroscopic measurements confirmed the identity of the synthetic compound with the natural product but with an opposite molecular rotation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Yuqing Chen, Shuangjie Lin, Fusheng Li, Xinhai Zhang, Luqing Lin, Lei Shi
Article
Chemistry, Multidisciplinary
Fusheng Li, Shuangjie Lin, Yuqing Chen, Caizhe Shi, Huaipu Yan, Chenchen Li, Chao Wu, Luqing Lin, Chunying Duan, Lei Shi
Summary: This study reports a novel photocatalytic strategy for the generation of pi-allyltitanium complexes, allowing for the rapid access to valuable homoallylic alcohols through a three-component allylation reaction with 1,3-butadiene and carbonyls. The exceptional regio- and diastereoselectivity provided by dual photoredox/Ti catalysis is comparable to that of the Cr-catalyzed Nozaki-Hiyama-Kishi allylation reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Fusheng Li, Shuangjie Lin, Xiyu Li, Lei Shi
Summary: This study introduces a novel radical strategy for the photocatalytic generation of pi-allyltitanium complexes from butadiene, enabling the direct three-component allylation of carbonyls. This environmentally benign approach provides rapid access to valuable homoallylic alcohols with exceptional regio- and diastereoselectivity control.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Physical
Caizhe Shi, Fusheng Li, Yuqing Chen, Shuangjie Lin, Erjun Hao, Zhuowen Guo, Urwa Tul Wosqa, Dandan Zhang, Lei Shi
Summary: This paper describes a photocatalytic umpolung strategy for the synthesis of nucleophilic allylcobalt complexes through a single-electron-transfer process, allowing the metallaphotoredox allylation of carbonyls with allyl acetate without the use of a stoichiometric amount of metals. UV-visible spectroscopy was used to monitor the redox changes of cobalt in the reaction.
Article
Chemistry, Organic
Shuangjie Lin, Yuqing Chen, Huaipu Yan, Yonghong Liu, Yuchen Sun, Erjun Hao, Caizhe Shi, Dandan Zhang, Nan Zhu, Lei Shi
Summary: Metallaphotocatalysis commonly requires light-absorbing metal-polypyridyl complexes, semiconductors, or organic dyes to modify the oxidation state of metal catalysts. However, this study demonstrates that photoexcitation of Hantzsch ester can directly activate chromium reagents through a single-electron transfer process, allowing for a synthetic application without the need for exogenous photocatalysts, metallic reductants, or additives in the decarboxylative allylation of aldehydes with butadiene as the feedstock.
Article
Chemistry, Multidisciplinary
Yuqing Chen, Huaipu Yan, Qian Liao, Dandan Zhang, Shuangjie Lin, Erjun Hao, Rukhsana Murtaza, Chenchen Li, Chao Wu, Chunying Duan, Lei Shi
Summary: In this study, we present a metal-free radical cross-coupling strategy for the synthesis of homoallyl amines. This method involves the reaction between an alpha-amino alkyl radical and a transient allylic radical to obtain homoallyl amines from readily available materials. The method exhibits excellent regioselectivity and broad functional group compatibility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Yonghong Liu, Shuangjie Lin, Dandan Zhang, Bingkun Song, Yunhe Jin, Erjun Hao, Lei Shi
Summary: This work presents a photochemical Nozaki-Hiyama-Kishi coupling reaction enabled by bioinspired Hantzsch ester, which serves as both an electron and a proton donor. The method offers a mild and operationally easy approach that shows broad compatibility with various alkenyl triflates and aldehydes.
Article
Chemistry, Multidisciplinary
Huaipu Yan, Qian Liao, Yuqing Chen, Gagik G. G. Gurzadyan, Binghui Lu, Chao Wu, Lei Shi
Summary: Co-porphines were discovered to be highly efficient MHAT catalysts for chemoselective allene functionalization under photoirradiation with a loading of only 0.01 mol %. The combination of photo Co-MHAT and Ti catalysis enabled successful carbonyl allylation, providing expedient access to beta-functionalized homoallylic alcohols in over 100 examples with exceptional regio- and diastereoselectivity. Mechanism studies supported the key role of selectively transferring hydrogen atoms from cobalt hydride to allenes and generating allyl radicals in the catalytic cycle.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Jinglan Lei, Min Li, Qingqing Zhang, Shuyang Liu, Haifang Li, Lei Shi, Wen-Feng Jiang, Chunying Duan, Yunhe Jin
Summary: We report a convenient and manipulable synthesis of methylenebisamide derivatives through visible-light-driven radical cascade reactions incorporating C(sp3)-H activation and C-N/ N-O cleavage. Mechanistic studies reveal the involvement of both a traditional Ir-catalyzed photoredox pathway and a novel copper-induced complex-photolysis pathway, enabling the activation of inert N-methoxyamides and the synthesis of valuable bisamides. This approach offers many advantages, including mild reaction conditions, broad scope and functional group tolerance, and competitive step economy. With its mechanistic plenitude and operational simplicity, we believe this method paves a promising way for the synthesis of valuable nitrogen-containing molecules.
Article
Chemistry, Organic
Erjun Hao, Binghui Lu, Yonghong Liu, Tianxiao Yang, Huaipu Yan, Xiaobo Ding, Yunhe Jin, Lei Shi
Summary: Recently, radical difunctionalization of 1,3-butadiene has gained attention as a strategy to increase molecular complexity. In this study, a novel approach combining radical thiol-ene chemistry with Ti-III catalysis under visible light conditions was developed for a three-component aldehyde allylation using 1,3-butadiene as an allyl group source. This sustainable and straightforward method allows for the rapid production of diverse allylic 1,3-thioalcohols with exceptional regio- and diastereoselectivity.
Article
Chemistry, Organic
Huaipu Yan, Jing-Ran Shan, Fengzhi Zhang, Yuqing Chen, Xinyi Zhang, Qian Liao, Erjun Hao, Lei Shi
Summary: A radical strategy using metal-hydride hydrogen atom transfer (MHAT) via photoredox cobalt and titanium dual catalysis is reported for alkene functionalization. The method achieves excellent regio- and diastereoselectivity.
Article
Chemistry, Multidisciplinary
Yonghong Liu, Huaipu Yan, Yuqing Chen, Erjun Hao, Lei Shi
Summary: This study describes a highly efficient method for the photoinduced copper-catalyzed 1,2-amino oxygenation of 1,3-dienes. The approach involves the use of a single copper catalyst, which serves as both a photosensitizer and a reactant with allyl radicals through single electron transfer (SET) processes. The method enables the synthesis of a variety of quaternary carbon-centered allyl carboxylic esters and tertiary ethers with high yields and excellent regioselectivity under mild reaction conditions.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Huaipu Yan, Jing-Ran Shan, Lei Shi
Summary: The metal-hydride hydrogen atom transfer (MHAT) method is a powerful technique for functionalizing alkenes. However, its application in industrial feedstock dienes and allenes is limited due to chemo-selectivity challenges. Recent studies have found that Co-porphines are highly efficient catalysts under photoirradiation, showing exceptional chemoselectivity for the functionalization of dienes and allenes.
Article
Chemistry, Organic
Fu-sheng Li, Yu-qing Chen, Shuang-jie Lin, Cai-zhe Shi, Xi-yu Li, Yu-chen Sun, Zhuo-wen Guo, Lei Shi
ORGANIC CHEMISTRY FRONTIERS
(2020)
Article
Chemistry, Multidisciplinary
Shuangjie Lin, Yuqing Chen, Fusheng Li, Caizhe Shi, Lei Shi
