Article
Chemistry, Organic
Zhi Zhang, Liansuo Zu
Summary: The study successfully synthesized a steroid-sterigmatocystin heterodimer using a concise method, including cascade dialdehyde cyclization, phenol-assisted reductive alkylation, and SNAr reaction. The research also explored a glycosylation-inspired method to provide the acetal linkage with ergosterol peroxide.
Article
Chemistry, Multidisciplinary
Kosuke Okada, Ken-ichi Ojima, Hirofumi Ueda, Hidetoshi Tokuyama
Summary: The synthesis of (+)-pleiocarpamine, (+)-voacalgine A and (+)-bipleiophylline was achieved in this study. The 10-step synthesis of (+)-pleiocarpamine features the construction of stereochemistry at the C16 position by radical cyclization and the synthesis of the highly strained cage-like structure via Pd-catalyzed intramolecular aromatic C-H functionalization. By modifying the biomimetic aerobic oxidative coupling of tryptophane derivatives catalyzed by FePc(CO2H)(8), the oxidative coupling of (+)-pleiocarpamine with pyrocatechuic acid produced (+)-voacalgine A. The total synthesis of (+)-bipleiophylline was completed by the second coupling of (+)-voacalgine A with (+)-pleiocarpamine or the one-pot couplings of 2 equiv of (+)-pleiocarpamine with pyrocatechuic acid.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Hesi Yang, Yan Zhang, Wei Chen, Hongliang Shi, Liang Huo, Jia Li, Huilin Li, Xingang Xie, Xuegong She
Summary: This article describes the first total syntheses of two novel ansamacrolactams, (+/-)-catellatolactams A and B, in 5 and 8 steps, respectively. The synthesis strategy involves an amidation reaction, a regioselective C-H insertion, and an RCM reaction to form the macrocycles with E-olefin. The concise and scalable synthesis provided over 200 mg of the target molecules.
Article
Chemistry, Multidisciplinary
Robert F. Lusi, Goh Sennari, Richmond Sarpong
Summary: A strategy orthogonal to classic approaches and coupled with C-H functionalization methods has been used to achieve the shortest synthesis and divergent syntheses of a sesquiterpenoid longiborneol, providing inspiration for the synthesis of other topologically complex natural products.
Article
Chemistry, Organic
Zhenyu Zhang, Wei Zhang, Jun-Chen Tang, Jin-Teng Che, Zhongchao Zhang, Jia-Hua Chen, Zhen Yang
Summary: The researchers synthesized (+)-Haperforin G in 20 steps from commercially available starting materials. They used a Co-catalyzed intramolecular Pauson-Khand reaction to selectively construct a cyclopentanone with an all-carbon quaternary stereogenic center at the bridge-head position. Light-initiated photocatalysis was employed for the convergent and asymmetric cross-coupling of the unstabilized C(sp(3)) radical with an enone. This developed chemistry opens up possibilities for synthesizing structurally diverse analogs of haperforin G (6).
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Lukas Anton Wein, Klaus Wurst, Thomas Magauer
Summary: The study presented the construction of seven novel ent-trachylobane diterpenoids using a bioinspired synthetic strategy. Enantioselective and scalable access to five ent-trachylobanes was achieved in the first phase, with one compound produced on a 300 mg scale. Chemical C-H oxidation methods were then used in the second phase to selectively convert two higher functionalized ent-trachylobanes, revealing the potential and limitations of established protocols for complex molecule synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
In-Soo Myeong, Nadide Hazal Avci, Mohammad Movassaghi
Summary: The first total synthesis of (-)-kopsifoline A and (+)-kopsifoline E was achieved in this study, featuring a biogenetically inspired regioselective C17-functionalization strategy for a versatile intermediate. The vinylogous urethane substructure of the intermediate allowed for the synthesis of (-)-kopsifoline D via C3-C21 bond formation under Mitsunobu reaction conditions, as well as selective C17-functionalization en route to (-)-kopsifoline A and (+)-kopsifoline E.
Article
Chemistry, Organic
Mizushi Yanagihara, Kanae Nakahara, Naoki Kishimoto, Towa Abe, Satoshi Miura, Shogo Misumi, Makoto Sako, Mitsuhiro Arisawa, Kenichi Murai
Summary: The first total synthesis of marine sesterterpenoid ansellone G and phorbadione was achieved, and their HIV latency-reversing activity was evaluated.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Mizushi Yanagihara, Kanae Nakahara, Naoki Kishimoto, Towa Abe, Satoshi Miura, Shogo Misumi, Makoto Sako, Mitsuhiro Arisawa, Kenichi Murai
Summary: The first total synthesis of marine sesterterpenoid ansellone G (2) has been accomplished. The hydrobenzopyran skeleton of ansellone G (2) was synthesized through the Prins cyclization reaction of a chloro-substituted homoallyl alcohol. The HIV latency-reversing activity of the synthesized compounds was also evaluated.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Lilla Koser, Thorsten Bach
Summary: The first total synthesis of (-)-5-deoxyenterocin has been accomplished, starting from pentane-1,3,5-triol with a linear sequence of 16 steps and an overall yield of 0.2%. Key steps of the synthesis include aldol reactions, hydroxylation reactions, and an intramolecular aldol reaction. Despite attempts, a functionalization reaction at position C5 was unsuccessful.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Haidi Tang, Muliang Zhang, Yuchao Zhang, Penghao Luo, Davide Ravelli, Jie Wu
Summary: Researchers have developed a method for synthesizing thioesters through carbonyl thiyl radical-based reactions, using direct photocatalyzed hydrogen atom transfer. This method allows for the synthesis of complex pharmaceutical molecules from readily available commodity chemicals. The study provides a new approach for the application of thiol-ene click chemistry in organic synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Adriana Recoba-Torres, Silvano Cruz-Gregorio, Leticia Quintero, Jacinto Sandoval-Lira, Julio Romero-Ibanez, Fernando Sartillo-Piscil
Summary: This report presents a new synthesis strategy for the direct deconstruction of a tetracyclic indoloquinolizine motif into the scaffold of a naturally occurring alkaloid, without the need for transition or precious metals.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Emily K. Kirkeby, Zachary T. Schwartz, Myles A. Lovasz, Andrew G. Roberts
Summary: This article presents a concise strategy for preparing polycyclic heteroaromatics through a deaminative contraction cascade. The efficient deaminative ring contraction involves the methylation and rearrangement/dehydroamination of a biaryl-linked dihydroazepine. The presence of pseudosymmetry guides the retrosynthetic analysis and allows for the construction of pyridyl-containing polycyclic heteroaromatics.
Article
Chemistry, Multidisciplinary
Emily K. Kirkeby, Zachary T. Schwartz, Myles A. Lovasz, Andrew G. Roberts
Summary: This article details a concise strategy to prepare polycyclic heteroaromatics through a deaminative contraction cascade. The efficient deaminative ring contraction involves the methylation of a biaryl-linked dihydroazepine to form a cyclic ammonium cation, followed by a base-induced [1,2]-Stevens rearrangement/dehydroamination sequence. The presence of pseudosymmetry guides the retrosynthetic analysis of pyridyl-containing polycyclic heteroaromatics, enabling their construction through reductive cyclization and deaminative contraction of tertiary amine precursors.
Article
Chemistry, Organic
Ze-Jun Xu, Xu-Yuan Liu, Ming-Zhu Zhu, Yu-Liang Xu, Yue Yu, Hai-Ruo Xu, Ai-Xia Cheng, Hong-Xiang Lou
Summary: In this study, two types of photoredox-catalyzed cascade reactions using diaryliodonium salts were developed for the concise synthesis of norascyronone A and beta-eudesmol. A rationally designed photoredox-catalyzed arylation/cyclization/Friedel-Crafts cascade reaction was used for the norascyronone synthesis, while a visible-light-induced radical cyclization/acyloxy-migration reaction was explored for the eudesmol synthesis, with mechanistic studies indicating initiation by one-electron oxidation of the enol ester.
Review
Chemistry, Multidisciplinary
Dongsheng Xue, Haibing He, Shuanhu Gao
Summary: This review highlights strategies for building the tetracyclic ring skeleton and the all-carbon quaternary center for total syntheses of wortmannin and viridin, which are furanosteroids with potential pharmaceutical applications.
Article
Chemistry, Organic
Chaoying Zheng, Tao Xie, Haibing He, Shuanhu Gao
Summary: A new approach was developed for the asymmetric total synthesis of (+)-PD-116740, involving a sequence of asymmetric dihydroxylation followed by oxidative cyclization. A new Cu salt was found to be the best oxidant for inducing the oxidative coupling and phenol oxidation, providing a valuable strategy for future pharmaceutical research.
Article
Chemistry, Organic
Kuanwei Chen, Tao Xie, Yanfang Shen, Haibing He, Xiaoli Zhao, Shuanhu Gao
Summary: The study describes the first asymmetric total synthesis and structural determination of calixanthomycin A, using a concise modular strategy to assemble the hexacyclic skeleton and stereoselective glycosylation. This approach enabled the determination and assignment of the absolute configuration of C-25 and the monosaccharide derivative of L-glucose.
Article
Chemistry, Multidisciplinary
Mengmeng Xu, Min Hou, Haibing He, Shuanhu Gao
Summary: This study developed a new synthetic method for constructing aryltetralin lactone lignans and successfully synthesized several natural lignans using this methodology. The synthesized aglacins and small-molecule library created new opportunities for SAR studies of the podophyllotoxin family of natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Zhengyuan Xin, Hui Wang, Haibing He, Xiaoli Zhao, Shuanhu Gao
Summary: The asymmetric total synthesis of norzoanthamine was achieved using radical reactions as key steps. This approach allowed for precise control of stereochemistry and construction of the highly congested heptacyclic skeleton, addressing a major synthetic challenge in most zoanthamine alkaloids.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Baochao Yang, Guoen Wen, Quan Zhang, Min Hou, Haibing He, Shuanhu Gao
Summary: Perovskones and hydrangenones are a family of structurally complex triterpenoids mainly isolated from Salvia medicinal plants, showing a wide range of biological activities such as antitumor and antiplasmodial activities. The total synthesis of these compounds involved asymmetric photoenolization/Diels-Alder reactions, bioinspired Diels-Alder reactions, and late-stage oxidations and ring forming steps. Studies suggest that perovskatone D may be a precursor for the biosynthesis of perovskones, while the formation of hydrangenone and hydrangenone B may involve an oxidative ring cleavage and ring regeneration process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Dongsheng Xue, Yonglei Que, Hao Shao, Haibing He, Xiaoli Zhao, Shuanhu Gao
Summary: The study on excited-state Nazarov reactions of dicyclicvinyl ketones showed their potential in synthesizing complex natural products, by constructing core tricyclic compounds with specific stereochemistry.
Article
Chemistry, Organic
Zhengyuan Xin, Hui Wang, Haibing He, Shuanhu Gao
Summary: This paper focuses on the importance of contiguous all-carbon quaternary centers in natural products and recent synthetic strategies used in total syntheses. By reviewing 12 representative synthetic examples, the power of these reactions in constructing such centers is showcased to inspire future exploration.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Shaolei Ding, Yingbo Shi, Baochao Yang, Min Hou, Haibing He, Shuanhu Gao
Summary: We describe the asymmetric total synthesis of periglaucines A-C, N,O-dimethyloxostephine and oxostephabenine. Key strategies include a regio- and diastereoselective Hayashi-Miyaura reaction, an intramolecular photoenolization/Diels-Alder reaction, and a bio-inspired intramolecular Michael addition and transannular acetalization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hui Wang, Yi Liu, Hongyuan Zhang, Baochao Yang, Haibing He, Shuanhu Gao
Summary: The asymmetric total syntheses of cephalotaxus C19 diterpenoids, which possess a unique cycloheptene A ring with a chiralmethyl group at C-12, were achieved using a universal strategy. Six members, including previously unreported compounds, were successfully synthesized. The concise approach involved a Nicholas/Hosomi-Sakurai cascade reaction to generate the cycloheptene ring with a chiral methyl group, followed by an intramolecular Pauson-Khand reaction for the construction of the target molecules' complete skeleton. This work provides a new strategy for the synthetic analysis of cephalotaxus diterpenoids and structurally related natural products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xiao-Long Lu, Yuanyou Qiu, Baochao Yang, Haibing He, Shuanhu Gao
Summary: The asymmetric total synthesis of (+)-xestoquinone and (+)-adociaquinones A and B was achieved in 6-7 steps using an easily accessible meso-cyclohexadienone derivative. The strategy provides a scalable route to prepare target molecules and their derivatives for further biological studies.
Article
Chemistry, Multidisciplinary
Min Hou, Mengmeng Xu, Baochao Yang, Haibing He, Shuanhu Gao
Summary: All-carbon quaternary stereocenters are common in natural products and drugs, but are challenging to construct due to their crowded chemical environment. A chiral titanium promoted enantioselective PEDA reaction has been developed to synthesize molecules with vicinal all-carbon quaternary centers, potentially facilitating the total synthesis of complex natural products or drug-like molecules.
Article
Chemistry, Organic
Xiao-Long Lu, Baochao Yang, Haibing He, Shuanhu Gao
Summary: An efficient approach to naphthol and naphthalene scaffolds has been developed using a sequence involving tandem Ti(Oi-Pr)(4)-promoted photoenolization Diels-Alder (PEDA) and aromatization reactions. This strategy was successfully utilized to synthesize the core skeletons of the bioactive marine natural products garveatin C and exiguaquinol.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Hongyuan Zhang, Haibing He, Shuanhu Gao
Summary: The asymmetric synthesis of the complex C-18 Cephalotaxus dinorditerpenoid cephanolide B was achieved for the first time using a remote hydroxyl group directed hydrogenation strategy and a sequence of modified transformations. The key hexahydrofluorenone core skeleton and selective reductions were crucial in achieving the target compound.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Review
Chemistry, Organic
Tao Xie, Haibing He, Shuanhu Gao
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2020)
