Article
Chemistry, Multidisciplinary
Shubham Dutta, Akhila K. K. Sahoo
Summary: This paper describes a Pd-catalyzed three-component syn-1,2-arylmethylation method, which successfully synthesizes methyl-containing tetra-substituted olefins by using readily available and stable coupling partners iodo-arenes and methyl boronic acid. The reaction shows a broad scope with excellent functional-group tolerance and exhibits remarkable regio- and stereoselectivity. Biologically relevant motifs (BRM) bearing iodo-arenes and ynamides are also used for late-stage syn-1,2-arylmethylation of alkynes. Additionally, aryl-alkylation, aryl-trideuteriomethylation, alkynyl-methylation, and alkenyl-methylation of ynamides are presented, leading to the synthesis of synthetically important beta-amino-indenones and alpha-fluoro-alpha '-methyl ketones.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Irene Martin, Cristina Aragoncillo, Pedro Almendros
Summary: This research has achieved a selective palladium-catalyzed reaction sequence, leading to the synthesis of novel 2-iodo-1-aryl-9H-carbazoles. The observed formation of 2-iodocarbazoles in contrast to gold catalysis suggests a metal-controlled cyclization through chemo- and regioselective alkyl migration and iodonium migration.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Multidisciplinary
Zhitong Zheng, Xu Ma, Xinpeng Cheng, Ke Zhao, Kaylaa Gutman, Tianyou Li, Liming Zhang
Summary: Homogeneous gold catalysis has seen significant development since the turn of the millennium, with oxidative gold catalysis being a vibrant subfield delivering valuable synthetic methods. This comprehensive review covers the mechanistic aspects, oxidants, and synthetic applications of oxidative gold catalysis.
Review
Chemistry, Physical
Bartolo Gabriele, Raffaella Mancuso, Nicola Della Ca, Lucia Veltri, Ida Ziccarelli
Summary: This article provides an overview of catalytic carbonylative double cyclization reactions, where organic substrates and carbon monoxide are sequentially activated to form two new cycles with the incorporation of carbon monoxide. It highlights the power of this synthetic methodology in the one-step synthesis of complex molecular architectures using readily available CO as the building block. The review is divided into five sections: Introduction, Functionalized Olefinic Substrates, Functionalized Acetylenic Substrates, Functionalized Halides, and Conclusions and Future Perspectives.
Review
Chemistry, Multidisciplinary
Kokila Sakthivel, R. J. Gana, Toshitaka Shoji, Naoko Takenaga, Toshifumi Dohi, Fateh V. Singh
Summary: This study demonstrates the effectiveness of metal catalysts in multicomponent reactions and provides an overview for their safe application in MCRs.
FRONTIERS IN CHEMISTRY
(2023)
Article
Chemistry, Applied
Seoyoung Lee, Juyeong Kim, Kyungjun Kang, Ansoo Lee, Hyunwoo Kim
Summary: In this study, we developed a ligand-controlled palladium-catalyzed allylic substitution approach that selectively achieves [1+1] and [1+2] allylic aminations between allylic diols and diamines. By combining this approach with sequential acetylation and allylic amination, tetraazamacrocycles with ring sizes ranging from 16 to 38 were successfully synthesized. These findings demonstrate the potential of a sequential allylation strategy for synthesizing complex molecules with broad applications in the fields of chemistry, pharmaceuticals, and medicine.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Nardana Sivendran, Nico Pirkl, Zhiyong Hu, Angelino Doppiu, Lukas J. Goossen
Summary: Halogen-bridged methylnaphthyl (MeNAP) palladium dimers, presented as versatile Pd precursors, demonstrate excellent catalytic performance by in situ conversion into well-defined monoligated complexes. They show benchmark activities in challenging reactions, enable record-setting yields, and can achieve previously elusive cross-couplings.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Peter Langer
Summary: The present article discusses the personalized Account on the synthesis of nitrogen heterocycles through domino C-N coupling/hydroamination reactions and related processes. The starting materials, 2-alkynyl-1-halohetarenes, are obtained regioselectively by Sonogashira reactions of various 1,2-dihalogenated heterocycles. The formation of more complex products is achieved through domino C-N coupling/hydroamination/C-H arylation reactions. These reactions result in the formation of new heterocyclic core structures with interesting pharmacological or fluorescence properties.
Article
Chemistry, Multidisciplinary
Barry M. Trost, Zhijun Zuo
Summary: A novel Pd-0-catalyzed highly selective [3+2] spiroannulation reaction has been developed for rapid assembly of a new class of [5,5] spirocyclic carbo- and heterocycles. The regioselectivity of the reaction can be controlled by fine-tuning the Pd-pi-allyl intermediate, with excellent toleration of various coupling partners and enantioselectivities demonstrated through further transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Han-Jun Ai, Wangyang Lu, Xiao-Feng Wu
Summary: Thiocarbonylation of alkynes offers a versatile method for the synthesis of unsaturated thioesters, with the possibility of controlling the product structure by using different ligands and acid additives. This approach also demonstrates the first example of thiocarbonylation of internal alkynes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Andrzej Zieba, Joel F. Hooper
Summary: A palladium-catalysed carboborylation reaction for the synthesis of borylated indanes has been investigated, showing good yields and tolerance to substitution on the aryl ring, but sensitivity to alkene substitution. Initial studies towards an enantioselective version of this reaction were undertaken, identifying phosphoramidites as a promising ligand class, allowing for the synthesis of chiral indane and indolone products with moderate levels of enantioselectivity.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Xavier Abel-Snape, Gina Wycich, Mark Lautens
Summary: A palladium-catalyzed three-component domino reaction for accessing indene derivatives is described. The reaction involves the sequential formation of three bonds, with the first two resulting from inter- and intramolecular carbopalladation, and the final bond arising from an attack by a terminating nucleophilic reagent. The starting tether on the iodoarene can be modified to yield either indenes or benzofulvenes. Additionally, the use of an oxabicycle as an acetylene surrogate is demonstrated, and the enantioselective synthesis of indenes is preliminarily explored.
Article
Chemistry, Multidisciplinary
Csaba Arvai, Laszlo T. Mika
Summary: This review summarizes the recent applications of alternative solvents in improving the efficiency, safety, and environmental friendliness of carbonylation reactions. The use of water, biomass-based alcohols, ionic liquids, and other alternative solvents can enhance the reaction protocols.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
James E. Baumann, Gojko Lalic
Summary: A new method for the differential dihydrofunctionalization of terminal alkynes has been developed, enabling the synthesis of allylic boronate esters through a reductive three-component coupling reaction. This transformation, promoted by a copper/palladium catalyst system, hydrofunctionalizes both pi-bonds of the alkyne. The method is compatible with a wide range of functional groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Raffaella Mancuso, Melania Lettieri, Ida Ziccarelli, Patrizio Russo, Antonio Palumbo Piccionello, Bartolo Gabriele
Summary: A catalytic carbonylative approach is presented for the multicomponent synthesis of benzothiophene derivatives, based on an S-cyclization-demethylation-alkoxycarbonylation-reduction sequence promoted by the PdI2/KI catalytic system under relatively mild conditions. Benzothiophene-2-acetic esters are obtained in moderate to good yields starting from variously substituted substrates in combination with different alcohols as external nucleophiles.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Inorganic & Nuclear
Linlin Shi, Yingdong He, Jianxian Gong, Zhen Yang
Summary: The efficient palladium-catalyzed decarboxylative cycloaddition process allows for the synthesis of highly substituted delta-lactone and delta-lactam derivatives. This method demonstrates broad substrate scope, good functional group tolerance, and operational convenience, enabling the regioselective access to a variety of lactone and lactam scaffolds in moderate to good yield. The redox-neutral catalytic system promotes the formation of substituted scaffolds with the in situ generation of a cyclic tetra-substituted double bond functionality.
Review
Chemistry, Multidisciplinary
Zhen Yang
Summary: The total synthesis endeavors contribute to the discovery and invention of new synthetic reactions to advance organic synthesis. Bioactive compounds share common features, such as molecular complexity, protein-binding ability, structural rigidity, and three-dimensionality. Total synthesis offers an alternative solution for generating scarce natural products and their derivatives for studying their biological functions.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Organic
Xin-Ting Liang, Bao-Chuan Sun, Nan Zhang, Zhong-Chao Zhang, Yuan-He Li, Qian-Qian Xu, Chang Liu, Jia-Hua Chen, Zhen Yang
Summary: The final phase of the total synthesis of (-)-spirochensilide A is described, utilizing a tungsten-mediated cyclopropene-based Pauson-Khand reaction, intermolecular aldol condensation, and Cu-mediated 1,4-addition to form the desired ring system and stereochemical centers. The developed chemistry will facilitate the synthesis of polycyclic natural products with a unique spiral ring system.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Xin-Ting Liang, Bao-Chuan Sun, Chang Liu, Yuan-He Li, Nan Zhang, Qian-Qian Xu, Zhong-Chao Zhang, Yi-Xin Han, Jia-Hua Chen, Zhen Yang
Summary: A concise and diastereoselective method has been developed for the construction of the key ring system of spirochensilide A, paving the way for the first asymmetric total synthesis of (-)-spirochensilide A.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Xin-Peng Mu, Yuan-He Li, Nan Zheng, Jian-Yu Long, Si-Jia Chen, Bing-Yan Liu, Chun-Bo Zhao, Zhen Yang
Summary: A novel method for the synthesis of cyclohepta[b]indoles in high yields was developed through a visible-light-induced, photocatalyzed [2+2]-cycloaddition/ retro-Mannich-type reaction of enaminones. Experimental and computational studies indicated that the reaction is initiated by single-electron oxidation of an enaminone moiety, leading to cyclobutane formation and rapid fragmentation in a radical-cation state to produce cyclohepta[b]indoles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Dian Li, Jinfeng Yang, Bingyan Liu, Jianxian Gong, Zhen Yang
Summary: A strategy for the stereoselective synthesis of desacyl furanmonogones A and B has been achieved, involving key steps such as Fe(ClO4)(3)-mediated oxidative radical cyclization, phosphorane-mediated rearrangement, and Au-catalyzed cascade reaction.
Article
Chemistry, Multidisciplinary
Jun Huang, Tingting Cao, Zhongchao Zhang, Zhen Yang
Summary: The article describes an enantioselective semisynthesis of (-)-bufospirostenin A, involving the use of biomimetic and diastereoselective reactions for construction of the bicyclic motif, and a Co-catalyzed reversible double-bond isomerization reaction for installing the double bond.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Anding Li, Ziru He, Bingyan Liu, Zhen Yang, Zichun Zhang
Summary: In this study, a concise and stereoselective total synthesis of (+/-)-cephanolide B was accomplished in 15 steps. The key steps in the synthesis included an intermolecular Diels-Alder reaction, a tandem reaction featuring intramolecular Pauson-Khand reaction, 6 pi-electrocyclization, and oxidative aromatization to construct the ABC-tricyclic rings (6-5-6), as well as a phthaloyl peroxide-mediated arene oxygenation to install the C-13 phenol group.
Article
Chemistry, Organic
Jiangqun Cheng, Yuan-He Li, Jun Huang, Zhen Yang
Summary: The diastereoselective syntheses of syn- and anti-vicinal dihalides were achieved through an aza Bellus-Claisen rearrangement, involving the reaction of an alpha-chloro carboxylic acid chloride with halogen-substituted trans-allyl morpholines in the presence of Lewis acids. This method was successfully applied to the total synthesis of a group of monoterpene natural products with vicinal dichloride subunits.
Article
Chemistry, Organic
Tingting Cao, Lei Zhu, Jun Huang, Zhen Yang
Summary: This study successfully installed a sterically congested all-carbon quaternary center for the first time via a Pd-catalyzed cascade diarylation, providing a new method for the synthesis of complex organic compounds.
Article
Chemistry, Organic
Lijie Zhang, Rongya Wang, Chao Wang, Bingyan Liu, Jinfeng Yang, Zhongchao Zhang, Jun Huang, Zhen Yang
Summary: A spiro-oxepin isoxazoline skeleton was synthesized via 1,3-dipole cycloaddition, enabling the total syntheses of 7-deoxyceratinamide A and 7-deoxypsammaplysins K and O.
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
Shu-Min Lu, Chao Chen, Chang Liu, Rudong Liu, Jia-Hua Chen, Zhongchao Zhang, Zhen Yang
Summary: Regioselective synthesis of 5,6,7-trihydroxyl and 5,7,8-trihydroxyl flavones was achieved using a transition-metal-catalyzed C-H oxidation with naturally enriched 5,7-dihydroxyl flavone as the starting material. This method was applied to the synthesis of biologically active flavonoids wogonin, oroxylin A, and their glycosylated derivatives as potential carnitine palmitoyltransferase 1 activators.
Article
Chemistry, Multidisciplinary
Hao-Yuan Liu, Zhen-Yu Zhang, Yi-Ke Zhou, Jia-Hua Chen, Zhen Yang, Yuan-He Li
Summary: This paper presents an efficient strategy for synthesizing the DEFGH rings of phainanoid F, involving a photo-induced electrocyclization and a homoallylic elimination. It is noteworthy that the electrocyclization reaction was used to simultaneously construct two vicinal quaternary carbons in total synthesis, which is a rare example. The strategy outlined here serves as the basis for the total synthesis of Phainanoid F and could be applied in synthesizing other natural products with similar 13,30-cyclodammarane skeletons.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Organic
Zhenyu Zhang, Wei Zhang, Jun-Chen Tang, Jin-Teng Che, Zhongchao Zhang, Jia-Hua Chen, Zhen Yang
Summary: The researchers synthesized (+)-Haperforin G in 20 steps from commercially available starting materials. They used a Co-catalyzed intramolecular Pauson-Khand reaction to selectively construct a cyclopentanone with an all-carbon quaternary stereogenic center at the bridge-head position. Light-initiated photocatalysis was employed for the convergent and asymmetric cross-coupling of the unstabilized C(sp(3)) radical with an enone. This developed chemistry opens up possibilities for synthesizing structurally diverse analogs of haperforin G (6).
JOURNAL OF ORGANIC CHEMISTRY
(2023)