Article
Chemistry, Multidisciplinary
Cheng Bi, Yu Wang, Chi He, Phil S. Baran
Summary: This paper reports a concise total synthesis of the complex guanidinium toxin KB343, achieved through a series of unusual chemoselective transformations and strategic skeletal reorganization. The absolute configuration is confirmed through an enantioselective route, and the structures of all key intermediates and the natural product itself are unequivocally confirmed through X-ray crystallographic analysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Applied
Masatoshi Yamada, Kazuki Azuma, Iori Takizawa, Yuki Ejima, Mitsuhisa Yamano, Kimio Satoh, Takayuki Doi, Hirofumi Ueda, Hidetoshi Tokuyama
Summary: A scalable asymmetric total synthesis of (-)-emetine, an important component in emetics, has been achieved. The synthesis involved 13 steps of highly efficient chemical reactions, including catalytic asymmetric allylation and industrial deoxygenation, eliminating the need for chromatographic purification. A high yield of (-)-emetine center dot 2HCl (12%) with over 93.2% HPLC purity was obtained, and the synthesis can be easily scaled up for larger production and currently used in natural ipecac syrup for clinical application.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2023)
Article
Chemistry, Multidisciplinary
Marko Nesic, David B. Ryffel, Jonathan Maturano, Michael Shevlin, Scott R. Pollack, Donald R. Gauthier Jr, Pablo Trigo-Mourin, Li-Kang Zhang, Danielle M. Schultz, Jamie M. McCabe Dunn, Louis-Charles Campeau, Niki R. Patel, David A. Petrone, David Sarlah
Summary: The collaborative total synthesis of darobactin A, a selective antibiotic against Gram-negative bacteria, has been achieved in a convergent manner using D-Garner's aldehyde and L-serine as starting materials. The synthesis involved 16 steps and three scalable routes were developed to synthesize non-canonical amino acids. The closure of the bismacrocycle was successfully achieved through sequential, halogen-selective Larock indole syntheses, with the cyclization order playing a crucial role in the formation of the desired atropisomer.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Minami Odagi, Taisei Matoba, Keisuke Hosoya, Kazuo Nagasawa
Summary: The first enantioselective total syntheses of hasubanan alkaloid (-)-metaphanine and norhasubanan alkaloid (+)-stephadiamine have been reported. These syntheses involve diastereoselective oxidative phenolic coupling reaction and subsequent regioselective intramolecular aza-Michael reaction to efficiently construct the hasubanan skeleton with a quaternary stereogenic center at C13. Furthermore, based on a hypothesis regarding the biosynthetic pathway of (+)-stephadiamine, it was found that (-)-metaphanine can easily be converted to (+)-stephadiamine via an aza-benzilic acid type rearrangement reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Liu-Yang Pu, Zhiyue Li, Limin Li, Yucui Ma, Shengquan Hu, Zhengzhi Wu
Summary: We report a concise asymmetric total synthesis of isopavine alkaloids, which possess a unique azabicyclo[3.2.2]nonane tetracyclic skeleton. The key steps involve iridium-catalyzed asymmetric hydrogenation of unsaturated carboxylic acids, Curtius rearrangement, and Eschweiler-Clarke methylation, achieving an enantioselective approach to isopavine alkaloids in 6-7 linear steps. Moreover, isopavine alkaloids, especially (-)-reframidine (3), are found to exhibit effective antiproliferative effects on various cancer cell lines for the first time.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Liu-Yang Pu, Zhiyue Li, Limin Li, Yucui Ma, Shengquan Hu, Zhengzhi Wu
Summary: In this study, we describe a concise and enantioselective total synthesis of isopavine alkaloids with a unique azabicyclo[3.2.2]nonane tetracyclic skeleton. Key steps include iridium-catalyzed asymmetric hydrogenation, Curtius rearrangement, and Eschweiler-Clarke methylation, enabling the synthesis of isopavine alkaloids in 6-7 linear steps. Additionally, we discovered that isopavine alkaloids, particularly (-)-reframidine (3), exhibit significant antiproliferative effects on various cancer cell lines for the first time.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Isaac D. Falk, Balint Gal, Ahanjit Bhattacharya, Jeremy H. Wei, Paula V. Welander, Steven G. Boxer, Noah Z. Burns
Summary: Archaeal glycerol dibiphytanyl glycerol tetraethers (GDGT) are unusual membrane lipids found in Archaea, including extremophiles. Interest in studying their biophysical properties and biosynthesis is high, but limited access to pure samples has hindered progress in this area. This study reports a concise synthesis method for archaeal tetraether lipid parallel GDGT-0 and derivatives with different polar groups for self-assembly.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Kenji Morokuma, Kento Tanaka, Raku Irie, Masato Oikawa
Summary: This study reports the design, synthesis, and double asymmetric hydrogenation of a racemic enamide for the stereodivergent synthesis of lycoperdic acid and its isomers. The hydrogenation outcome was used to identify matched and mismatched products, providing important information for clarifying the reaction mechanism. It is also suggested that knowing the reaction mechanism can help determine the structure of the products without spectroscopic analyses, based on the matched/mismatched analysis.
Article
Chemistry, Multidisciplinary
Dongyu Sun, Ruyi Chen, Dongmin Tang, Qidong Xia, Yifan Zhao, Chun-Hui Liu, Hanfeng Ding
Summary: This article describes the asymmetric total synthesis of (-)-retigeranic acid A, which relies on a crucial reductive skeletal rearrangement cascade for the controllable assembly of diverse angular triquinane subunits. Combined with an intramolecular Michael/aldol cyclization, an ODI-[5 + 2] cycloaddition/pinacol rearrangement cascade, a Wolff ring contraction, and a stereoselective HAT reduction, our synthetic approach has enabled the access to (-)-retigeranic acid A in a concise and practical manner.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yunpeng Ji, Benke Hong, Ivan Franzoni, Mengyang Wang, Weiqiang Guan, Hongli Jia, Houhua Li
Summary: In this paper, a 9-step enantioselective total synthesis of (+)-hyperforin and (+)-pyrohyperforin was described, starting from commercially available allylacetone. The synthesis involved important reactions such as the enantioselective deconjugative alpha-alkylation using chiral lithium amides as stereodirecting auxiliaries, the HfCl4-mediated carbonyl alpha-tert-alkylation to form the intricate bicyclo[3.3.1]nonane framework, an abiotic cascade pyran formation, and a selective 1,4-semihydrogenation of polyenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Inorganic & Nuclear
Vladimir B. Kharitonov, Dmitry V. V. Muratov, Dmitry A. Loginov
Summary: This review comprehensively summarizes the use of cyclopentadienyl complexes of Group 9 metals in the total synthesis of natural compounds, including catalyzing cycloaddition, transfer hydrogenation, and C-H activation reactions.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Zhuang Chen, Kuan Zhao, Yanxing Jia
Summary: This study presents a bioinspired total synthesis of (+)-euphorikanin A, which features a fascinating and intricate tetracyclic skeleton with a bridged [3.2.1]-gamma-lactone moiety. Key transformations involve stereoselective alkylation and aldol condensation to introduce the main stereocenters, an intramolecular nucleophile-catalyzed aldol lactonization of carboxylic acid-ketone to form the five-membered ring, a McMurry coupling to construct the seven-membered ring, and a biomimetic benzilic acid type rearrangement to generate the bridged [3.2.1]-gamma-lactone moiety.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Alexander W. Rand, Kevin J. Gonzalez, Christopher E. Reimann, Scot t C. Virgil, Brian M. Stoltz
Summary: Strempeliopidine, a member of the monoterpenoid bisindole alkaloid family, can modulate protein-protein interactions in human cancer cells. Our synthesis involved the installation of all-carbon quaternary centers using palladium-catalyzed decarboxylative asymmetric allylic alkylations. The final synthetic sequence used diastereoselective Petasis borono-Mannich reaction to connect eburnamine to a trifluoroborate aspidospermidine derivative. These convergent approaches supported the reassignment of the absolute configuration of strempeliopidine.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Ruben L. H. Andringa, Niels A. W. Kok, Arnold J. M. Driessen, Adriaan J. Minnaard
Summary: Ir-catalyzed asymmetric alkene hydrogenation combined with an established C-13-NMR method can effectively synthesize saturated isoprenoids and mycoketides, significantly improving synthetic efficiency.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Rodney A. Fernandes
Summary: Divergent synthesis of natural products is an important method for achieving synthesis efficiency and economy. By identifying advanced intermediates with specific structural features, the synthesis of multiple natural products can be achieved. Recent research has made significant progress and provides guidance for future development.
CHEMICAL COMMUNICATIONS
(2023)
