Article
Chemistry, Multidisciplinary
Yuan Jin, Kensuke Orihara, Fumiki Kawagishi, Tatsuya Toma, Tohru Fukuyama, Satoshi Yokoshima
Summary: The total synthesis of Haliclonin A was achieved through a series of reactions including Birch reduction/alkylation, ring-closing metathesis, intramolecular cyclopropanation, and stereoselective 1,4-addition, leading to the formation of the desired compound.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Alexander J. Hughes, Steven D. Townsend
Summary: In this study, we achieved the gram-scale total synthesis of (+/-)-ibogamine in nine steps and with an overall yield of 24%. The key steps include a Mitsunobu fragment coupling and macrocyclic Friedel-Crafts alkylation to establish the nitrogen-containing core of ibogamine. Additionally, a regio- and diastereoselective hydroboration reaction was used to simultaneously form the tetrahydroazepine and isoquinuclidine ring systems via sulfonamide deprotection and intramolecular cyclization.
Article
Chemistry, Organic
Gihan C. Dissanayake, Cornelius N. Ndi, Jana L. Markley, James B. Martinez, Paul R. Hanson
Summary: Two synthetic strategies involving phosphate tether-mediated one-pot sequential protocols were developed for the total synthesis of sanctolide A, a polyketide nonribosomal peptide macrolide, and the formal synthesis of its (2S)-epimer.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Andrew G. Dalling, Georg Spath, Alois Furstner
Summary: This article reports the first total synthesis of a tetracyclic marine pyridinium alkaloid, which was achieved using recent advances in chemoselectivity management. The synthesis involved the formation of critical C-C bond using nickel/iridium photoredox dual catalysis, successful ring closing alkyne metathesis (RCAM) despite the presence of a Lewis acidic alkylidyne catalyst, and a unique iridium catalyzed hydrosilylation reaction. The synthesis also demonstrated site- and chemoselective intramolecular N-alkylation for closing the second strained macrocycle.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Thomas Varlet, Soren Portmann, Alois Fuerstner
Summary: In this study, the first total synthesis of the cytotoxic marine natural product njaoamine C was achieved using double ring closing alkyne metathesis (dRCAM). Unlike previous approaches, both macrocyclic rings were formed simultaneously. The success of this synthesis was attributed to dynamic covalent chemistry and the chemoselectivity of palladium-catalyzed hydrostannation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Qiaoqiao Ao, Hai-Jun Zhang, Jinbin Zheng, Xiaoming Chen, Hongbin Zhai
Summary: The first asymmetric total synthesis of (+)-Mannolide C has been achieved through key transformations such as lipase-mediated resolution, Ru-complex-catalyzed double ring-closing metathesis (RCM) reactions, Ni-II-catalyzed diastereoselective Michael addition, and Mn-III-catalyzed allylic oxidation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Jason An, Richard K. Jackson, Joseph P. Tuccinardi, John L. Wood
Summary: This paper presents an efficient, scalable, and concise approach for the synthesis of an advanced pyrroloiminoquinone synthetic intermediate (6b) using Larock indole synthesis. The synthetic utility of this intermediate is demonstrated by its ready conversion to makaluvamines A (1) and K (4).
Article
Chemistry, Organic
Chong Li, Zhi-Chao Qi, Jing-Yu Li, Shang-Dong Yang
Summary: A novel method for P-involved heterocycle ringclosing-ring-opening rearrangement (HRR) via the Heck reaction has been disclosed, enabling direct installation of a phosphorus-containing aryl group onto the C2 position of indole with high yields. This new rearrangement provides a simple and efficient approach for the synthesis of indolyl-derived phosphonates and phosphinic acids.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Frank Schmidt, Aparna Viswanathan Ammanath, Friedrich Goetz, Martin E. Maier
Summary: A new synthesis route was established for the macrolactone antibiotic berkeleylactone A. The synthesis involved ring-closing alkyne metathesis (RCAM) of an ester substrate with 1-propynyl termini. The carboxylic part of the substrate was assembled using alkyne chemistry, while the alcohol part of the ester was synthesized through propylene oxide opening and triple bond migration reactions. After successful RCAM, the triple bond was selectively hydrogenated and the 4,5-diol was oxidized to obtain the desired derivative. The thioether formation and reduction of the 8,9-double bond were also achieved. However, the antimicrobial activity of the analog was found to be slightly reduced.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ya-Kui Sun, Jin-Bao Qiao, Yu-Meng Xin, Qin Zhou, Zhi-Hua Ma, Hui Shao, Yu-Ming Zhao
Summary: In this paper, a concise and divergent synthesis of the complex hasubanan alkaloids metaphanine and oxoepistephamiersine from commercially available and inexpensive cyclohexanedione monoethylene acetal is reported. The synthesis involves a palladium-catalyzed cascade cyclization reaction, regioselective Baeyer-Villiger oxidation followed by a MeNH2 triggered skeletal reorganization cascade, and a strategically late-stage regio-/diastereoselective oxidative annulation of sp(3) C-H bond. Additionally, a highly enantioselective alkylation of cyclohexanedione monoethylene acetal was used for the asymmetric synthesis of the target molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ya-Kui Sun, Jin-Bao Qiao, Yu-Meng Xin, Qin Zhou, Zhi-Hua Ma, Hui Shao, Yu-Ming Zhao
Summary: A concise and divergent synthesis of the complex hasubanan alkaloids metaphanine and oxoepistephamiersine from commercially available and inexpensive cyclohexanedione monoethylene acetal was reported. The synthesis includes a palladium-catalyzed cascade cyclization reaction, a regioselective Baeyer-Villiger oxidation followed by a MeNH2 triggered skeletal reorganization cascade, and a strategically late-stage regio-/diastereoselective oxidative annulation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Andrea Ojeda-Porras, Remi Aouzal, Claire Wilson, Joelle Prunet
Summary: Two synthetic routes for the ABC tricycle of Taxol are presented, both involving a relay ring-closing metathesis reaction to form the central B ring. In the first approach, the extender arm is positioned on the A ring, while the C ring bears the relay tether in the second route. Despite the efficient synthesis of metathesis precursors with diverse extender arms, the crucial metathesis reactions failed to yield the target compounds in all cases.
Article
Chemistry, Multidisciplinary
Jiujian Ji, Jiajun Chen, Sixun Qin, Wanye Li, Jun Zhao, Guozhao Li, Hao Song, Xiao-Yu Liu, Yong Qin
Summary: This article reports the first total synthesis of vilmoraconitine using efficient ring-forming reactions. Key steps include an oxidative dearomatization-induced Diels-Alder cycloaddition, a hydrodealkenylative fragmentation/Mannich sequence, and an intramolecular Diels-Alder cycloaddition.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Nicole Hauser, Michael A. Imhof, Sarah S. Eichenberger, Tomas Kundig, Erick M. Carreira
Summary: The first total syntheses of the indole diterpenoids (+)-shearinine G and D were achieved through late-stage coupling, diastereoselective intramolecular cyclopropanation, Sharpless dihydroxylation/Achmatowicz reaction, and Prins cyclization. Tuning of the substituents on the parent arylcarboxaldehyde led to divergent products, further transformed into shearinines G and D, with unexpected stereochemical outcomes in the Riley-type oxidation of a bicyclic enone.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yecai Lai, Wei-Min Dai
Summary: A pentamodule assembly approach has been developed for the total synthesis of (-)-palmyrolide A and (+)-5,7-epi-palmyrolide A. The flexibility of the multimodule assembly strategy for diverted total synthesis is demonstrated by the ability to obtain two diastereoisomeric macrolides from the same sequence of reactions.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Xiu-Ning Hu, Dong-Ping Wu, Ye-Peng Xu, Pei-Qiang Huang
Summary: The first organocatalytic asymmetric synthesis of an advanced intermediate of (+)-sarain A was achieved by combining organocatalytic asymmetric Michael addition reaction and a nitrogen-to-carbon chirality transfer. This method allows for the construction of three chiral centers and chemoselective reduction of a key lactam intermediate, providing a tricyclic intermediate with all necessary functionalities for further elaboration into (+)-sarain A.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Dong-Huang Chen, Wei-Ting Sun, Cheng-Jie Zhu, Guang-Sheng Lu, Dong-Ping Wu, Ai-E Wang, Pei-Qiang Huang
Summary: The combination of transition-metal catalysis and organocatalysis has enabled chemists to achieve direct enantioselective reductive cyanation and phosphonylation of secondary amides, synthesizing enantioenriched chiral alpha-aminonitriles and alpha-aminophosphonates for the first time. The protocol is efficient, enantioselective, scalable, and the thiourea catalyst can be recycled and reused.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Ya-Qing Huang, Xiong-Zhi Huang, Pei-Qiang Huang
Summary: A two-step approach was developed for the synthesis of bicyclic and monocyclic 5-(1-alkoxyalkylidene)tetronates from lactones/esters, featuring the use of thionolactones and thionoesters as activated forms. This method was demonstrated to be valuable through the stereoselective synthesis of two natural products.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Su-Yu Huang, Long-Hui Gao, Xiong-Zhi Huang, Pei-Qiang Huang
Summary: This article provides a detailed account of the synthetic efforts towards the enantioselective total synthesis of the complex alkaloid methoxystemofoline. The key steps include Keck allylation, olefin cross-metathesis, regioselective aldol addition, and Overman's method for moiety installation. The final step resulted in the formation of both the proposed structure of methoxystemofoline and its E-stereoisomer in a 1:1 ratio, leading to the suggestion to rename the natural product as isomethoxystemofoline.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Lian-Dong Guo, Zejun Xu, Rongbiao Tong
Summary: The asymmetric total syntheses of three paspaline-derived IDTs were reported, featuring green Achmatowicz rearrangement/bicycloketalization and cascade ring-closing metathesis of dienyne, as well as four palladium-mediated reactions. These synthetic strategies are expected to facilitate the chemical synthesis of other paspaline-derived IDTs and further bioactivity studies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Lixin Liang, Lian-Dong Guo, Rongbiao Tong
Summary: The six-membered heterocycles containing oxygen and nitrogen are commonly found in bioactive molecules and the chemical synthesis of fully functionalized pyrans and piperidines has attracted interest from synthetic chemists. The Achmatowicz rearrangement represents a unique strategy using biomass-derived furfuryl alcohols as starting materials, providing opportunities for addressing synthetic challenges. This Account summarizes the work done on exploiting AchR to address challenges in various organic synthesis, focusing on green chemistry, organic methodology, and total synthesis of natural products.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Organic
Dong-Ping Wu, Wei Ou, Pei-Qiang Huang
Summary: This study describes the catalytic reductive condensation reactions between tertiary amides and active methylene compounds, leading to multifunctionalized non-N-containing products. The reactions proceed through a sequential process involving iridium-catalyzed hydrosilylation of the amides followed by acid-mediated condensation with the active methylene compounds. This scalable method demonstrates a broad scope and remarkable chemoselectivity for the amide group in the presence of various sensitive or even more reactive functionalities such as ester, cyano, nitro, silyl dienol ether, and ketone.
Article
Chemistry, Organic
Jingping Hu, Lian-Dong Guo, Wenqing Chen, Yuyang Jiang, Fan Pu, Chengqing Ning, Jing Xu
Summary: This study reports the first total syntheses of daphnezomine L-type alkaloids, including daphnezomine L methyl ester and calyciphylline K, via late-stage C-N bond activation and a similar strategy for the synthesis of secodaphniphylline-type alkaloid caldaphnidine D. Other key transformations employed in the synthesis include a facile vicinal diol olefination and an efficient radical cyclization cascade. Biological studies indicate that the two synthetic compounds show promising neuroprotective activity.
Article
Multidisciplinary Sciences
Hang Chen, Zhi-Zhong Wu, Dong-Yang Shao, Pei-Qiang Huang
Summary: The catalytic asymmetric geminal bis-nucleophilic addition to nonreactive functional groups is a highly desirable yet challenging transformation in organic chemistry. In this study, the first catalytic asymmetric reductive/deoxygenative alkynylation of secondary amides was reported. The method combines iridium/copper relay catalysis with organocatalysis and allows the efficient synthesis of a variety of chiral a-branched amines. The protocol also demonstrates excellent enantioselectivity, chemoselectivity, and functional group tolerance.
Article
Chemistry, Multidisciplinary
Kan-Lei Ji, Shu-Fan He, Dong-Dong Xu, Wen-Xin He, Jian-Feng Zheng, Pei-Qiang Huang
Summary: A concise asymmetric total synthesis of (-)-quinocarcin has been achieved through high step economy using commercially available starting materials. The key chiral pyrrolidine intermediate with three stereocenters was prepared via a catalytic enantioselective reductive 1,3-dipolar cycloaddition reaction. This synthesis also involved a Rh-III-catalyzed C-H activation/cyclization and a tandem diastereoselective hydrogenation/cyclization to construct the tetrahydroisoquinoline-pyrrolidine tetracyclic core unit of quinocarcin.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Fang-Fang Xu, Jin-Quan Chen, Dong-Yang Shao, Pei-Qiang Huang
Summary: The study presents a unified strategy for the synthesis of various alkaloids using readily available amides and alkynes, which is important for drug and agrochemical discovery.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Hang Chen, Dong-Huang Chen, Pei-Qiang Huang
Summary: This study demonstrates the catalytic intermolecular decarbamoylative C-C arylation and C-B borylation of N-acylpyrrole-based tertiary amides using nickel,N-heterocyclic carbene (NHC) catalysis. The research is significant for the direct transformation of amides.
CELL REPORTS PHYSICAL SCIENCE
(2023)
Article
Chemistry, Organic
Si-Jia Yu, Jie Li, Jian-Liang Ye, Pei-Qiang Huang
Summary: A one-pot reaction using palladium catalyst has been developed for the synthesis of bicyclic 1,3-oxazin-4-ones, 2,3,6,7-tetrahydrocyclopenta[e]-1,3-oxazin-4-ones and 2,3,5,6,7,8-hexahydro-4H-benzo[e]-1,3-oxazin-4-ones. The reaction shows good yields, broad substrate scope, mild reaction conditions, and scalability. It also demonstrates good compatibility with acetyl chloride and phenylacetyl chloride for the synthesis of monocyclic 1,3-oxazin-4-ones.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Lian-Dong Guo, Yanting Wu, Xin Xu, Zhenyang Lin, Rongbiao Tong
Summary: This article presents a new synthetic strategy for the asymmetric total synthesis of spirohexenolides A and B. By designing ring-closing metathesis and double dehydration reactions, the C15 macrocycle with deformed nonplanar 1,3,5-triene conjugation was achieved. In vitro studies demonstrated cytotoxicity of both spirohexenolides against human cancer cells, with spirohexenolide A exhibiting higher activity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hui-Rong Lu, Hui Geng, Guan-Tian Ding, Pei-Qiang Huang
Summary: We report a catalyst- and solvent-free method to synthesize enantioenriched secondary amides. The method is simple, mild, versatile, and efficient with high selectivity, and can be applied to different types of asymmetric products and alpha-branched primary amines.
