Article
Chemistry, Multidisciplinary
Gleb A. Chesnokov, Karl Gademann
Summary: The marine-derived compound Peyssonnoside A was successfully synthesized for the first time in a concise, efficient, scalable, and highly diastereoselective manner. The aglucone peyssonnosol was achieved in 21% overall yield after 15 steps, with key reactions including Simmons-Smith cyclopropanation and Mukaiyama hydration controlled by the spatial structure of the substrates.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
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, 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, Multidisciplinary
Atsushi Nakayama, Tenta Nakamura, Toshihiro Zaima, Saho Fujimoto, Sangita Karanjit, Kosuke Namba
Summary: The concise total synthesis of tronocarpine, a chippiine-type indole alkaloid, was achieved through a one-pot construction of a pentacyclic skeleton. This strategy, controlled by the stereocenter at the C14 position, can be used to synthesize other chippiine-type alkaloids with azabicyclo[3.3.1]nonane skeletons.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Hai-Hua Lu, Kang-Ji Gan, Fu-Qiang Ni, Zhihan Zhang, Yao Zhu
Summary: The concise total synthesis of salimabromide was achieved using a series of novel reactions, which allowed for the construction of its unique carbon skeleton and stereocenters.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Hong-Gang Cheng, Zhenjie Yang, Ruiming Chen, Liming Cao, Wen-Yan Tong, Qiang Wei, Qingqing Wang, Chenggui Wu, Shuanglin Qu, Qianghui Zhou
Summary: A concise total synthesis of (-)-berkelic acid is reported in eight linear steps, featuring a Catellani reaction/oxa-Michael cascade, a one-pot deprotection/spiroacetalization operation, and a late-stage Ni-catalyzed reductive coupling. Notably, four stereocenters are established from a single existing chiral center with excellent stereocontrol during the deprotection/spiroacetalization process, supported by DFT calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Tufan K. Mukhopadhyay, Dirk Trauner
Summary: A general strategy to quickly access glycerophospholipids is reported in this study, utilizing the opening of a phosphate triester epoxide with carboxylic acids catalyzed by Jacobsen's Co(salen) complex. This method allows for the synthesis of various glycerophosphate derivatives.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Meng-Yue Cao, Bin-Jie Ma, Qing-Xiu Gu, Bei Fu, Hai-Hua Lu
Summary: This paper reports a concise protecting-group-free total synthesis of Daphenylline, a structurally unique member of the triterpenoid Daphniphyllum natural alkaloids. Key reactions include an intramolecular oxidative dearomatization reaction, a tandem reductive amination/amidation double cyclization reaction, and a highly enantioselective rhodium-catalyzed hydrogenation reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Huan He, Fanglin Xue, Zhao Hu, Peng Li, Qian Xiao, Maojie Zhang, Fei Xue, Dan Zhang, Hao Song, Xiao-Yu Liu, Zhibing Zheng, Song Li, Wu Zhong, Yong Qin
Summary: Morphine and its related alkaloids are commonly used natural medicines. However, the current industrial manufacturing process of these compounds causes environmental issues. In this study, researchers developed an efficient total synthesis method for opioids such as codeine, oxycodone, naloxone, and naltrexone. The key step in this synthesis is the Pd-catalyzed dearomatization arene coupling reaction using an inexpensive and stable phosphonium ligand.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Wei Xu, Taimin Wang, Xin Zhou, Lijing Fang, Chen Zhang, Hongbin Zhai, Bin Cheng
Summary: A concise total synthesis of (+/-)-pileamartines A and B, alkaloids with an unprecedented tetracyclic skeleton, was achieved. Key steps including NHC-catalyzed tandem reaction, diastereoselective reductive allylation, and RCM were used to establish the core structure.
ORGANIC CHEMISTRY FRONTIERS
(2022)
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
Chemistry, Multidisciplinary
Fuhao Zhang, Jingwen Zeng, Mohan Gao, Linzhou Wang, Gen-Qiang Chen, Yixin Lu, Xumu Zhang
Summary: A practical synthetic strategy for enantioselective and divergent synthesis of prostaglandins was reported, involving the construction of multiply substituted five-membered rings through key enyne cycloisomerization and installation of crucial chiral centers using asymmetric hydrogenation. Common intermediates allowed for the production of various prostaglandins and related drugs in two steps, with the preparation of fluprostenol on a 20-gram scale.
Article
Chemistry, Organic
Yuichiro Kawamoto, Hideki Kitsukawa, Toyoharu Kobayashi, Hisanaka Ito
Summary: The enantioselective total synthesis of nesteretal A was accomplished in 15 steps through biomimetic cascade hemiacetalizations, along with other key features like Sharpless asymmetric dihydroxylation, diastereoselective 1,2-addition, Pd-catalyzed ene-type cyclization, and stereoselective epoxidation to construct a complex structure containing multiple quaternary carbons.
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, Organic
Ningtao He, Jilong Zhang, Xiaohe Miao, Dehai Li, De Wang
Summary: In this study, the first organophosphine-catalyzed allylic alkylation of (hetero)arylalkynes with various carbo-nucleophiles is described. The method is highly atom economical and compatible with a wide range of substrates, leading to the concise total synthesis of natural product (& PLUSMN;)-esermethole.
