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, Multidisciplinary
Nathanyal J. Truax, Safiat Ayinde, Jun O. Liu, Daniel Romo
Summary: A pharmacophore-directed retrosynthetic strategy was applied to achieve the total synthesis of cembranoid rameswaralide. The synthesis involved a Diels-Alder lactonization process and rares kinetic resolution to construct the 5,5,6- and 5,5,7-tricyclic ring systems present in several Sinularia soft coral cembranoids. A pivotal intermediate, a tricyclic epoxy abromo cycloheptenone, displayed high cytotoxicity and enabled the pursuit of three unique D-ring annulation strategies. The serendipitous discovery of an oxidation state transposition facilitated the introduction of the required a-methylene butyrolactone.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(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, Organic
Shan-Shan Li, Li-Li Zhao, Min Pan, Na Feng, Bao-Qiong Li, Xiang-Zhi Zhang, Jin-Bao Peng, Ai-Jun Ma
Summary: An efficient synthesis of (+)-peniciketal B has been achieved in 15 steps from commercially available materials. A concise synthetic approach employing a cascade reaction was used to construct the benzo-fused 2,8-dioxabicyclo[3.3.1]-nonane with excellent stereoselectivity. The generality of the transformation was demonstrated by the broad scope of potential candidates for natural product synthesis and medicinal chemistry.
Review
Chemistry, Organic
Sun Yangxing, Li Yanzhi, Cao Yanlai, Wang Nengzhong, Xiang Shaohua, Liu Mingguo, Yao Hui
Summary: Carbohydrates are not only important as an energy source, but also play a crucial role in physiological activities and drug development. Glycosylation, the core reaction of carbohydrate chemistry, still poses a challenge in developing a general and efficient stereoselective glycosylation method. This article summarizes the development of functional groups on glycosyl donors in stereoselective regulation, focusing on their participation in glycosylation reactions through neighboring-group participation, remote group participation, intramolecular aglycone delivery, coordination, and hydrogen-bonding mediation.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Shuntao Huang, Qi Yang, Juan Wan, Zhuoyu Wang, Zhou Zhang, Teng Liu, Chao Huang
Summary: A concise and flexible protocol to assemble structurally diverse 1H-pyrrolo[3,4-b]quinoline-1,3(2H)-diones (29 examples, 70-87% yields) has been developed via one-pot stepwise synthesis. The potentially valuable quinine-fused heterocycles were synthesized by utilizing aliphatic alcohol hydroxyl as a directing group and undergoing an I-2-oxidized tandem annulation. This route involves the formation of multiple new chemical bonds (C=N, 2C-N, C-C) in a one-pot fashion under mild conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Rodney A. Fernandes, Dnyaneshwar A. Gorve, Amit K. Jha
Summary: A stereodivergent protecting-group-directed Tsuji-Trost cyclization has been successfully used to synthesize both 2,5-cis- and 2,5-trans-disubstituted-THF scaffolds. In the presence of a beta-O-silyl group, cis-2,5-disubstituted-3-oxygenated THF is formed with a high diastereomeric ratio of up to 9:1. Alternatively, when the free OH at the beta-position can coordinate with acetate, trans-2,5-disubstituted-3-hydroxy THF scaffold is generated as a single diastereomer (diastereomeric ratio up to 1:0). These THF scaffolds were used in the total synthesis of oxylipids and (+)-petromyroxol.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Kazuki Nakazato, Mami Oda, Haruhiko Fuwa
Summary: An 11-step synthesis of (+)-neopeltolide was developed using a tandem macrocyclization/transannular pyran cyclization strategy for stereo-controlled construction of the neopeltolide macrolactone. The C1-C7 carboxylic acid and the C8-C16 alcohol were prepared in six steps from (R)- and (S)-epichlorohydrin, respectively. The side chain was synthesized in six steps from ethyl 4-oxazolecarboxylate through palladium-catalyzed cross-couplings. The synthesis was completed by a Mitsunobu reaction of the neopeltolide macrolactone and the side chain.
Article
Chemistry, Multidisciplinary
K. C. Nicolaou, Saiyong Pan, Yogesh Shelke, Dipendu Das, Qiuji Ye, Yong Lu, Susanta Sau, Ruiyang Bao, Stephan Rigol
Summary: A new strategy for the total synthesis of Halichondrin B was described in this study, presenting a novel approach that allows for improved syntheses of complex compounds. The method involves the reversal of sequential construction and the coupling of defined fragments to achieve a convergent pathway.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Biochemistry & Molecular Biology
Xing-Yong Liang, Jing Yang, Zhong-Hao Qiu, Lei Wang, Todd L. Lowary, Hua-Jun Shawn Fan
Summary: This study developed a method for preparing 2-deoxy-2-azido-alpha-D-galactopyranosidic bonds using donor 5, which exhibited good to excellent alpha-selectivity attributed to specific protecting groups. The presence of TBDPS on 3-O and benzylidenyl on 4,6-di-O enhanced the activity of the thioglycoside and improved stereoselectivity, as demonstrated through the synthesis of a alpha-galactosamine-containing pentasaccharide 26.
CARBOHYDRATE RESEARCH
(2021)
Review
Biochemistry & Molecular Biology
Weicheng Zhang
Summary: The Heck macrocyclization reaction is an extension of the award-winning Mizoroki-Heck reaction, forming macrocycles by linking two coupling partners. This method has become a viable option for synthesizing diverse macrocycles and is significant in natural product synthesis.
NATURAL PRODUCT REPORTS
(2021)
Review
Chemistry, Multidisciplinary
Alexia N. Kim, Aurapat Ngamnithiporn, Emily Du, Brian M. Stoltz
Summary: This review discusses the general structure and biosynthesis of THIQ alkaloids and provides an overview of recent advancements in their total synthesis from 2002 to 2020. It highlights novel synthetic designs and modern chemical methodologies used in recent chemical syntheses.
Article
Chemistry, Organic
Yunhui Wan, Huaimo Wu, Linhao Xia, Song Liu, Yi Ren, Hongxi Xu, Changwu Zheng
Summary: A unified approach for the construction of the bicyclo[3.3.1]nonane-2,4,9-trione core of polycyclic polyprenylated acylphloroglucinols (PPAPs) was reported. This method involves sequential Dieckmann condensation reactions and has been successfully applied to the synthesis of various natural and synthetic compounds. Key steps of this approach include oxidative olefin cleavage and decarboxylative allylation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Dong-Yang Shao, Pei-Qiang Huang
Summary: We report the first synthesis of (4S,5S)-4-hydroxy-5-octylpyrrolidin-2-one, one of the colibactin pathway metabolites isolated and characterized in 2021. Through a concise synthetic approach, the enantioselective total synthesis of this natural product was achieved, providing full physical and spectral data.
Review
Chemistry, Multidisciplinary
Lu Liu, Minghua Jiang, Qingkang Zhang, Hong Chen, Yifu Zhang, Jian Zhang
Summary: This paper summarizes the asymmetric synthesis strategies of halichlorine and pinnaic acid, two structurally related natural alkaloids with diverse biological effects. The unique structure and potential biological activity of these compounds have attracted significant synthetic interest, making them a research focus in recent years. The review provides guidance for related work by highlighting the use of a 6-azaspiro[4.5]decane skeleton as a key intermediate in the synthesis strategies.