Review
Chemistry, Multidisciplinary
Jiawei Sun, He Yang, Wenjun Tang
Summary: This tutorial review summarizes the total synthesis of complex dimeric natural products and discusses various dimerization strategies. By highlighting selected representative examples, it aims to demonstrate the recent tactics of dimerization and provide insights on structural and chemical properties of related natural products, promoting advancements in organic synthesis and biological studies.
CHEMICAL SOCIETY REVIEWS
(2021)
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)
Review
Electrochemistry
Chad E. Hatch, William J. Chain
Summary: Electrochemical techniques have played a crucial role in the total synthesis of natural products since the pioneering work of Kolbe in the mid 1800s. These techniques have expanded over time, changing the way chemists approach and think about natural products. This review provides a perspective on the use of electrochemical techniques in enabling carbon-carbon bond formations in the assembly of important natural products, discussing mechanistic details and showcasing representative examples from the past few decades. These bond formations offer unique possibilities compared to conventional chemistries, allowing for complementary synthetic strategies.
Article
Chemistry, Organic
Jackson A. Gartman, Uttam K. Tambar
Summary: The scientific community has shown great interest in anthraquinone-based compounds due to their therapeutic properties and challenging structural elements. In recent decades, various architecturally beautiful natural products have been synthesized using two main strategies, either through early-stage synthesis of anthraquinone and further system elongation, or late-stage introduction of the anthraquinone ring moiety. This article describes selected syntheses of complex anthraquinone monomers and dimers from the past 20 years, with a focus on the retrosynthetic disconnections that shape the anthraquinone-installation strategy.
Article
Chemistry, Multidisciplinary
Hongchang Tian, Yinxia Wu, Xiujuan Li, Zhen Hao, Wenyan He, Xiangdi Huang, Wen Chen, Hongbin Zhang
Summary: In this article, we present the first total synthesis of Kopsaporine related alkaloids. Our structure-unit-based strategy utilizes intramolecular Pummerer rearrangement induced nucleophilic cyclization/aza-Prins cyclization to construct the hexahydrocarbazole skeleton, olefin migration vinylogous alkylation to establish the C20 all-carbon quaternary center, iridium complex mediated radical addition to fuse the aspidofractine framework, unprecedented IBX oxidation to introduce the alpha-hydroxyketone moiety, and bioinspired retro-Aldol/Aldol reaction to convert kopsaporine to kopsiloscine A.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Biochemistry & Molecular Biology
Yusuke Ogura
Summary: Dihydro-beta-agarofuran (DH beta AF) sesquiterpenoids, with their pharmacologically and agriculturally important biological properties, have attracted significant attention from synthetic organic and medicinal chemists. Recent advancements in stereoselective protocols have enabled the scalable total synthesis of these compounds, leading to the synthesis of complex natural derivatives.
BIOSCIENCE BIOTECHNOLOGY AND BIOCHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Jing Chen, Yangyang Jiang, Jialei Yan, Chao Xu, Tao Ye
Summary: The first total syntheses of cyclic depsipeptides colletopeptide A and colletotrichamide A have been achieved through a series of transformations. By constructing a cyclic tridepsipeptide derivative as a key intermediate, followed by late-stage incorporation of the mannose fragment, the synthesis of colletotrichamide A and desilylation of the common intermediate led to the confirmation of the absolute stereochemistry of the natural products.
Article
Chemistry, Organic
Leah J. Salituro, Jessica E. Pazienza, Scott D. Rychnovsky
Summary: This study reports the first total syntheses of strasseriolide A and B. Strasseriolide B exhibits potent activity against the wild-type malaria parasite Plasmodium falciparum and good activity against a chloroquine-resistant strain. A convergent strategy was employed, utilizing an aldehyde-acid fragment and a vinyl iodide-alcohol fragment, both prepared from chiral pool starting materials. The fragments were combined through a Yamaguchi esterification and cyclized with a Nozaki-Hiyama-Kishi reaction, resulting in the assembly of strasseriolide B in a 16-step LLS.
Article
Chemistry, Multidisciplinary
Shaobin Su, Chengcheng Lin, Hongbin Zhai
Summary: In this study, the total syntheses of (-)-daphnezomines A and B and (+)-dapholdhamine B have been successfully achieved in 16-20 steps through rapid construction of a common core intermediate. Key steps include the synthesis of the azabicyclo[3.3.1]nonane ring system, installation of the bridgehead all-carbon quaternary stereocenter, construction of the aza-adamantane backbone, and assembly of the (+)-dapholdhamine B backbone through 6-endo-trig aminocyclization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Haruka Fujino, Masanori Nagatomo, Masayuki Inoue
Summary: Hikizimycin is a potent anthelmintic and antibacterial natural product with a complex structure that has attracted synthetic chemists since its structural determination in the early 1970s. Efforts have culminated in synthetic approaches including the synthesis of protected hikosamines and total synthesis of Hikizimycin, showcasing the evolution of modern natural product synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yan Zong, Ze-Jun Xu, Rong-Xiu Zhu, Ai-Hong Su, Xu-Yuan Liu, Ming-Zhu Zhu, Jing-Jing Han, Jiao-Zhen Zhang, Yu-Liang Xu, Hong-Xiang Lou
Summary: An enantioselective synthetic approach for preparing manginoids and guignardones, two types of biogenetically related meroterpenoids, is described in this study. The bioinspired and divergent synthesis involves an oxidative 1,3-dicarbonyl radical-initiated cyclization and cyclodehydration of a common precursor to forge the central ring of the manginoids and guignardones. Key synthetic steps include silica-gel-promoted semipinacol rearrangement and the Suzuki-Miyaura reaction of vinyl bromide for fragment coupling, enabling the asymmetric syntheses of four fungal meroterpenoids from commercially available materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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
Wu Hou, Xin Cao, Peng Xu, Biao Yu
Summary: In this study, the synthesis of two tetranorditerpenoid dilactones, Wentilactones A and B, with promising antitumor activities is reported for the first time. The synthesis involves the use of a common precursor, 3 beta-hydroxydilactone 6, derived from (S)-Wieland-Miescher ketone, and allows for easy modification on the A-ring, resulting in compounds such as CJ-1445, asperolide B, and an unnamed natural congener 4.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Baiyang Jiang, Mingji Dai
Summary: We report the total syntheses of four hamigeran natural products with a 6-7-5 tricyclic carbon skeleton. A palladium-catalyzed intramolecular cyclopropanol ring-opening cross-coupling was used to build the central seven-membered ring, and a series of oxidations, including a challenging aromatic C-H oxidation, were employed to introduce the peripheral functionalities. This approach allowed us to achieve the first total syntheses of hamigeran C (14 steps), debromohamigeran I (12 steps), hamigeran I (13 steps), and hamigeran G (13 steps), significantly shorter than the previously reported longest linear sequence (24 steps).
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Christian Steinborn, Tatjana Huber, Julian Lichtenegger, Immanuel Plangger, Klaus Wurst, Thomas Magauer
Summary: The first asymmetric total synthesis of waixenicinA, a potent TRPM7 inhibitor, was achieved. The synthesis involved the construction of a characteristic trans-fused oxabicyclo[7.4.0]-tridecane ring system through a diastereoselective conjugate addition/trapping sequence, followed by an intramolecular alkylation to form a 9-membered ring. The synthesis also employed a beta-keto sulfone motif for efficient ring-closure and a fluoride-mediated decarboxylation to prevent isomerization. Additionally, a base-mediated rearrangement reaction led to the synthesis of xeniafaraunol A.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
