Article
Chemistry, Multidisciplinary
Huy Tran, Guillaume Revol, Alyson Poyser, Louis Barriault
Summary: In this study, a novel Lewis acid gold catalyst was used to generate synthetically challenging polycyclic scaffolds through a one-pot cascade sequence. By controlling the ligand and reaction conditions, both 6,6,5-tricyclic and 6,6,6,5-tetracyclic cores were selectively synthesized in one operation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Jian-Xiang Zhu, Fu Pi, Teng Sun, Wen-Yu Huang, Lu Gao, Zhi-Chao Chen, Wei Du, Ying-Chun Chen
Summary: This article introduces a palladium-catalyzed tandem reaction that proceeds through sequential 2,4-dienylation/Michael addition/pi-sigma-pi isomerization/allylic alkylation. Using ortho-functionalized aryl enones and 2,4-dienyl carbonates as substrates, enantioenriched architectures with fused and spirocyclic frameworks are constructed in moderate to excellent yields and stereoselectivity. Importantly, the intrinsic intramolecular Diels-Alder reaction pattern of the dienylated intermediates is effectively reversed via Pd(0)-pi-Lewis base catalysis.
Article
Chemistry, Multidisciplinary
Kyu-Hyun Sim, Thameem ul Ansari, Yong-Gyu Park, Yeolib Jeong, Sang-Ha Oh, Hye-Won Min, Da-Yoon Jeon, Hyunwoo Kim, Cheon-Gyu Cho
Summary: This study reports the intramolecular Diels-Alder reactions of 2-pyrones with a chiral branched allylic silyl ether substituent, showing remarkably high pi-facial- and endo-selectivities. The resulting diastereomerically and enantiomerically pure cycloadducts were transformed into the natural products (+)-lycopladine A and (-)-lycoposerramine R.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Guang-Chao Feng, Jun-Chi Li, Xiang Huang, Ji-Kai Liu, Bin Wu, Jin-Ming Yang
Summary: A novel cascade gold(I)-catalyzed hydroarylation of alkynylindoles and subsequent Diels-Alder cycloaddition with electron-deficient alkynes and alkenes is reported herein. The method features low catalyst loadings, high regioselectivity, broad functional group tolerances, access to important heterocycles, and 100% atom economy.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Shuheng Xu, Linwei Zeng, Sunliang Cui
Summary: The Diels-Alder (DA) reaction and hetero-Diels-Alder (HDA) reaction are powerful methods for constructing carbocycles and heterocycles. This study presents an integrated building block that combines both DA and HDA reactions, utilizing triazenyl dienes to undergo the DA reaction and the newly released alkene moiety and triazene to engage in the HDA reaction.
Article
Chemistry, Applied
Luke D. Elliott, Kevin Booker-Milburn, Alastair J. J. Lennox
Summary: This study demonstrates a rare example of a photo/thermal daisy-chained process, with the first visible-light-mediated excited state coupled with thermal cascade reaction conducted as a fully continuous process. The synthetic utility of flow chemistry is further showcased by the isolation of a reactive intermediate at quantities not possible under batch conditions.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Article
Chemistry, Multidisciplinary
Sarah A. French, Christopher J. Sumby, David M. Huang, Jonathan H. George
Summary: Inspired by a new biosynthetic hypothesis, a biomimetic total synthesis of atrachinenins A and B was achieved, explaining their racemic nature, and also suggesting a structure revision for atrachinenin C.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Casper Larsen Barlose, Jonas Faghtmann, Rene Slot Bitsch, Joseph Daniel Gbubele, Karl Anker Jorgensen
Summary: The combination of asymmetric organocatalysis with the (pseudo)-halogen effect allows for the efficient formation of chiral norcarane scaffolds. These scaffolds can easily undergo rearrangements or lactonization to form intricate chiral ring structures.
Article
Chemistry, Organic
Flavie Rambaud, Regis Guillot, Valerie Alezra, Cyrille Kouklovsky
Summary: A cycloaddition-fragmentation sequence involving benzene oxide and a nitroso- or azo-dienophile was studied for the synthesis of highly substituted cyclohexene oxide derivatives. The alkyl lithium-promoted fragmentation of the cycloadducts resulted in cyclic derivatives through 1,4- or 1,2-addition of a second equivalent of the lithium reagent. The use of non-nucleophilic bases of hindered alkyl lithium reagents led to new fragmentation processes. All reactions exhibited complete stereocontrol.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Ruyu Xie, Zhiqiang Zhao, Yongxing Zhao, Rui Li, Jinzhong Yao, Maozhong Miao
Summary: Via Cu(I)-catalyzed cycloisomerization, readily available allenyl ketones bearing a cyclopropyl moiety can form in situ furan-fused cyclobutenes, which are highly reactive and powerful species that can undergo annulative fragmentation with terminal ynones to produce a wide variety of functional furans in moderate to high yields. This ring-distortion protocol features an unprecedented strain-controlled cycloisomerization/Diels-Alder/retro-Diels-Alder (CDRD) sequence under mild conditions.
Article
Chemistry, Multidisciplinary
Zorana Ferjancic, Andrej Kukuruzar, Filip Bihelovic
Summary: An enantioselective total synthesis of the monoterpenoid indole alkaloid (+)-alstonlarsine A (1) has been achieved, which possesses a unique pentacyclic skeleton and rare biological activity. The key step involves an efficient domino sequence, consisting of enamine formation followed by an inverse-electron-demand intramolecular dearomative Diels-Alder cycloaddition for the construction of a 9-azatricyclo[4.3.1.0(3,8)]decane core. This strategy offers a new general entry into other tricyclic frameworks with fused indole ring and 6-, 7-, or 8-membered rings.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Tsai-Hui Lung, Yi-Ru Chen, Chen-Ling Chang, Wey-Chyng Jeng, Pei-Shan Wu, Sandip Sambhaji Vagh, Gangababu Marri, Yi-Fang Lin, Wenwei Lin
Summary: A catalyst-controlled diversity-oriented synthesis of spirohydroquinoline-indandiones and 3-methylenehydroquinoline-indandiones was reported using ortho-sulfonamidophenyl-substituted para-quinone methides and allylidene-indandiones. Organobases such as DMAP or TMG were utilized to selectively control the reaction pathway, resulting in products with yields of 40-99% and excellent diastereoselectivities. Mechanistic studies revealed that spirohydroquinoline-indandione was the kinetic product, which underwent an unusual base-initiated 1,3-nitrogen rearrangement process to afford 3-methylenehydroquinoline-indandione in the presence of TMG.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Maciej Saktura, Sebastian Frankowski, Bartlomiej Joachim, Lukasz Albrecht
Summary: The study presents a method for aminocatalytic synthesis of highly enantiomerically enriched uracil derivatives with a bicyclo[2.2.2]octane scaffold, utilizing various aminocatalytic activation strategies for stereoselective construction. The reaction cascade involves doubly cycloadditive steps with dearomatization of the uracil moiety, and excellent stereoselectivity is achieved using 2-(diphenylmethyl)pyrrolidine as aminocatalyst.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Jonathan P. Knowles, Hannah G. Steeds, Maria Schwarz, Francesca Latter, Kevin Booker-Milburn
Summary: This method transforms simple starting materials into complex tetracyclic products with potential medicinal chemistry applications through a sophisticated chemical catalysis process.
Article
Chemistry, Multidisciplinary
Guanghao Huang, Cyrille Kouklovsky, Aurelien de la Torre
Summary: The first enantioselective total synthesis of (+)-lucidumone is described, involving key steps such as an enantioselective inverse-electron-demand Diels-Alder cycloaddition and C-O bond formation. The synthesis is scalable and produced over one gram of natural product in one batch.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Hao Wang, Yuzhen Gao, Chunlin Zhou, Gang Li
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Multidisciplinary
Zhuomin Chi, Yuzhen Gao, Lei Yang, Chunlin Zhou, Meng Zhang, Peiming Cheng, Gang Li
Summary: A visible-light-induced spirocyclizative hydroarylation via reductive dearomatization of non-activated arenes, including 2-phenyl indoles and naphthalene derivatives, is described. This protocol allows for the rapid synthesis of valuable spirocycles with carbon-carbon double bonds from readily accessible aromatic precursors in a single step.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Shangda Li, Chunhui Zhang, Lei Fu, Hang Wang, Lei Cai, Xiaoxi Chen, Xinchao Wang, Gang Li
Summary: Metathesis reactions are powerful synthetic tools used in various fields. In this study, the first Pd(II)-catalyzed C-H iodination of arenes was reported, using 2-nitrophenyl iodides as iodinating reagents via a formal metathesis reaction. The reaction exhibited unusual C-I bond formation instead of C-C coupling, allowing for selective iodination of challenging substrates.
Article
Chemistry, Multidisciplinary
Yuzhen Gao, Hao Wang, Zhuomin Chi, Lei Yang, Chunlin Zhou, Gang Li
Summary: In this paper, a novel strategy for visible-light-induced spirocyclizative remote arylcarboxylation of nonactivated arenes is reported. This transformation, achieved through a radical-polar crossover cascade, allows for the rapid synthesis of diverse spirocyclic and carboxylic acid derivatives from readily accessible aromatic precursors.
Article
Chemistry, Organic
Ning Wang, Zhuomin Chi, Xinchao Wang, Zezhong Gao, Shangda Li, Gang Li
Summary: Functional group metathesis has the potential to provide mild reaction conditions for C-H functionalization. This study reports the meta- and ortho-C-H iodination of aniline derivatives using 2-nitrophenyl iodides as mild iodinating reagents. The results demonstrate the potential for developing novel site-selective C-H activation reactions with electron-rich compounds using mild reagents.
Article
Chemistry, Organic
Zezhong Gao, Hang Wang, Chunlin Zhou, Ning Wang, Shangda Li, Gang Li
Summary: In this study, a new C-H functionalization method was reported for the remote site-selective C-H iodination via C(sp(2))-H/C(sp(2))-I metathesis. The mild iodinating reagent, 1-iodo-4-methoxy-2-nitrobenzene, was used to iodinate 2-aryl benzoic acid derivatives, including 2-(naphthalen-1-yl)benzoic acids and [1,1'-binaphthalene]-2-carboxylic acids, giving valuable iodinated products in a site- and chemo-selective manner.
Article
Chemistry, Physical
Hang Wang, Huiling Li, Xiahe Chen, Chunlin Zhou, Shangda Li, Yun-Fang Yang, Gang Li
Summary: In this study, a chiral ligand-controlled, asymmetric remote meta-C-H activation method was reported. By using a specific chiral ligand and Pd(II) catalyst, asymmetric C-H olefination and arylation of arenes were achieved. The origins of enantioselectivity were explained through density functional theory calculations.
Article
Chemistry, Multidisciplinary
Hong Lv, Xinchao Wang, Yanzhao Hao, Chao Ma, Shangda Li, Gang Li, Jian Zhang
Summary: A new method for carboxylation of unactivated sp(2) C-H bonds with CO2 was reported using a rhodium catalyst, generating a series of ferrocene-embedded lactones that are important molecular skeletons in pharmaceuticals and ligands. The first example of asymmetric C-H carboxylation with CO2 was achieved with a chiral NHC ligand, demonstrating moderate enantioselectivity. Preliminary mechanistic experiments revealed bivalent rhodium as the active catalyst, and a reasonable catalytic cycle was proposed.
Article
Chemistry, Multidisciplinary
Hang Wang, Chunlin Zhou, Zezhong Gao, Shangda Li, Gang Li
Summary: In this study, a highly enantioselective isodesmic C-H functionalization method was developed to access chiral iodinated phenylacetic Weinreb amides via desymmetrization and kinetic resolution with Pd-II catalysis. The rapid synthesis of chiral aromatic iodides is of significant importance for synthetic chemistry, and further transformations of the enantioenriched products are readily available, opening up new possibilities for related studies in synthetic and medicinal chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Lei Yang, Xinchao Wang, Meng Zhang, Shangda Li, Xinqiang Fang, Gang Li
Summary: This study reports a Pd-catalyzed remote isodesmic meta-C-H iodination of phenethylamines, benzylamines, and 2-aryl anilines using 1-iodo-4-methoxy-2-nitrobenzene as the mild iodinating reagent. A range of valuable meta-iodinated and even multi-halogenated amines were successfully synthesized, paving the way for synthetic chemists to access various amine derivatives at the challenging meta-positions.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Hang Wang, Huiling Li, Xiahe Chen, Chunlin Zhou, Shangda Li, Yun-Fang Yang, Gang Li
Summary: The use of a chiral ligand-controlled, asymmetric remote meta-C-H activation enables asymmetric C-H olefination and arylation of hydrocinnamic acid derivatives. The origins of the enantioselectivity were explained using density functional theory calculations.
Article
Chemistry, Multidisciplinary
Hao Wang, Lei Fu, Chunlin Zhou, Gang Li
Summary: The newly developed Pd-catalyzed meta-C-H bromination of aniline derivatives overcomes the ortho/para selectivity competition in electrophilic bromination, with the addition of acid additives crucial for reaction success. A broad range of substrates and benzoic acid derivatives with complex substitution patterns are applicable, with the potential for C-H chlorination under similar conditions.
Article
Chemistry, Multidisciplinary
Chunlin Zhou, Xinchao Wang, Lei Yang, Lei Fu, Gang Li
Summary: This study reports a method of using light to drive a regioselective carbocarboxylation reaction between CO2 and aryl and alkyl halides. This method allows for the rapid and highly regioselective synthesis of complex β,γ-unsaturated carboxylic acids.
Article
Chemistry, Multidisciplinary
Xinchao Wang, Hang Wang, Chunlin Zhou, Lei Yang, Lei Fu, Gang Li
Summary: This study presents a method of employing a native directing group for C-H activation, specifically focusing on the ortho-C-H acetoxylation of hydrocinnamic and phenylacetic acids, which are key moieties in many biologically active molecules. The broad scope and potential application of this reaction, as demonstrated with drug molecules, indicate its promising utility in future synthetic endeavors.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Xiaoxi Chen, Shuai Fan, Meng Zhang, Yuzhen Gao, Shangda Li, Gang Li
Summary: An unprecedented pyridine-based para-directing template (DT) assisted, Pd-catalyzed para-C-H alkenylation of three classes of arenes was reported, which allows for easy synthesis and recycling under mild conditions. This method offers a new approach for the rapid construction of para-substituted arenes.
