Article
Chemistry, Organic
David L. Cain, Niall A. Anderson, David B. Cordes, Alexandra M. Z. Slawin, Allan J. B. Watson
Summary: A concise strategy for the total synthesis of several Aspidosperma alkaloids has been reported. The strategy involves a Suzuki-Miyaura cross-coupling and a Diels-Alder cascade reaction, leading to the synthesis of a common intermediate for Aspidosperma alkaloids. This intermediate has been successfully utilized for the synthesis of four different natural products.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Nicholas L. Magann, Mitchell T. Blyth, Michael S. Sherburn
Summary: The concise synthesis of alkaloid lythranidine utilizes the target's C-2 symmetry, adopting a two directional synthetic approach to efficiently access gram quantities of the natural product. The broad-spectrum nature of the synthesis is demonstrated through the preparation of three diastereomeric analogues of the natural product.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Mezna Saleh Altowyan, Saied M. Soliman, Matti Haukka, Nora Hamad Al-Shaalan, Aminah A. Alkharboush, Assem Barakat
Summary: In this study, a novel heterocyclic hybrid of a spirooxindole system was synthesized by attaching ferrocene and triazole motifs into an azomethine ylide through a [3 + 2] cycloaddition reaction. The X-ray structure analysis revealed the expected structure of the heterocyclic hybrid and its crystallization in the triclinic-crystal system. Hirshfeld analysis provided insights into the molecular packing and identified the dominant intermolecular contacts in the crystal structure. AIM study indicated covalent characteristics for the Fe-C interactions.
Article
Chemistry, Organic
Lu Yang, Siwen Huang, Rongkang Huang, Anbin Hou, Sen Zhang, Hongwei Su, Xiaohong Ding, Bin Lin, Maosheng Cheng, Yongxiang Liu
Summary: The total syntheses of aspidospermidine and its derivatives were achieved from a common pentacyclic indoline intermediate through complex organic synthesis methods, providing an important foundation for further research on this class of indole alkaloids.
Review
Chemistry, Multidisciplinary
Long Min, Li-Ping Zhong, Chuang-Chuang Li
Summary: Steroids continue to play a significant role in organic chemistry, medicinal chemistry, and drug discovery. However, the synthesis of unusual rearranged steroids, particularly abeo-steroids with a medium-sized ring, remains a challenge. This Account summarizes the laboratory's efforts in the total synthesis of abeo-steroids using cycloaddition strategies, highlighting the efficiency and versatility of each strategy in constructing structurally complex abeo-steroid cores. The findings provide valuable insights for advancing the total synthesis of abeo- and related steroids.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Physical
Ken Yamazaki, Pablo Gabriel, Graziano Di Carmine, Julia Pedroni, Mirxan Farizyan, Trevor A. Hamlin, Darren J. Dixon
Summary: This study discusses an iridium-catalyzed method for the reductive generation of azomethine ylides and their use in pyrrolidine synthesis. The method allows for the efficient access to structurally complex pyrrolidine architectures through subsequent dipolar cycloaddition reactions with variously substituted electron-deficient alkenes. Density functional theory calculations reveal the control of unusual selectivities observed in certain cases by an intimate balance between asynchronicity and interaction energies of transition structures in the cycloaddition reactions.
Article
Chemistry, Multidisciplinary
Kristen M. Flynn, In-Soo Myeong, Taylor Pinto, Mohammad Movassaghi
Summary: We report the total synthesis of complex aspidosperma alkaloids (-)-voacinol and (-)-voacandimine C using a biogenetic hypothesis-inspired synthetic strategy. By chemoselective oxidation and methylenation reactions, we synthesized a versatile precursor that enabled the access to these natural alkaloids. The final-stage controlled reductive opening of a dodecacyclic intermediate led to a unified approach for the synthesis of (-)-voacinol and (-)-voacandimine C.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Biochemistry & Molecular Biology
Saman Sayebani, Hossein Eshghi, Maryam Naeimabadi
Summary: A new and diverse route has been developed for synthesis of novel pyrrole derivatives using azomethine ylides. The azomethine ylides are produced via C-H activation and then reacted with olefins to form pyrrole derivatives. This synthetic method shows moderate to excellent yields in experiments.
MOLECULAR DIVERSITY
(2022)
Article
Biochemistry & Molecular Biology
Valeriia V. Sennikova, Alena Zalaltdinova, Yulia M. Sadykova, Ayrat R. Khamatgalimov, Almir S. Gazizov, Alexandra D. Voloshina, Anna P. Lyubina, Syumbelya K. Amerhanova, Julia K. Voronina, Elena A. Chugunova, Nurbol O. Appazov, Alexander R. Burilov, Michail A. Pudovik
Summary: We present a regio- and diastereoselective synthesis of novel pyrrolidine-fused spiro-dihydrophosphacoumarins through intermolecular [3 + 2] cycloaddition reaction. This method complements existing approaches and provides an easy way to obtain otherwise inaccessible derivatives. Additionally, we describe the unprecedented pathway of the reaction between 4-hydroxycoumarin and azomethine ylides. The most potent compound showed 2.6-fold higher anti-cancer activity against the HuTu 80 cell line compared to 5-fluorouracil, with a selectivity index > 32.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Physical
Mohammad Shahidul Islam, Matti Haukka, Saied M. Soliman, Abdullah Mohammed Al-Majid, A. F. M. Motiur Rahman, Ahmed Bari, Assem Barakat
Summary: A novel synthesis method for spirooxindoles engrafted with pyrazole skeleton was reported, using a one-pot multicomponent [3 + 2] cycloaddition reaction transformation. The regio- and diastereo-selectivity of the spiroheterocycles were elucidated through X-ray diffraction analysis, revealing the impact of short distance contacts on molecular packing and crystal stability. DFT calculations and NMR spectra analysis indicated the polar nature and electronic properties of the compounds, with good correlations between calculated and experimental data.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Organic
Sami Ben Salah, Morgane Sanselme, Yves Champavier, Mohamed Othman, Adam Daich, Isabelle Chataigner, Ata Martin Lawson
Summary: An efficient 1,3-dipolar cycloaddition was reported, involving non-stabilized electron-rich azomethine ylides and diversely substituted 2-pyridones bearing two potential C=C dipolarophilic sites. The reactions occur under mild conditions, leading to the expected cycloadducts with good yields and full control of the regioselectivity. Furthermore, the diastereoselectivity of the second cycloaddition was fully controlled by the first addition, resulting in tricyclo-adducts with a trans relative stereochemistry.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Zhigang Chen, Wei Zhong, Sihua Liu, Ting Zou, Kaiqiang Zhang, Chuliang Gong, Wenyan Guo, Feizhi Kong, Libo Nie, Shunqin Hu, Haifei Wang
Summary: In this study, we report the highly diastereo- and enantioselective [3 + 2] cycloadditions of iminoesters with various alpha-substituted acrylates. The reactions are catalyzed by AgHMDS/DTBM-Segphos or Ag2O/CA-AA-Amidphos, and result in the stereodivergent synthesis of chiral C4-ester-quaternary exo- or endo-pyrrolidines with high yields and excellent diastereo- and enantioselectivities (up to >99:1 dr and >99% ee). The gram-scale synthetic exo-adduct is particularly significant, as it enables the total synthesis of the spirotryprostatin A alkaloid in nine steps with a 36% overall yield.
Article
Biochemistry & Molecular Biology
Richa Sharma, Lalit Yadav, Ali Adnan Nasim, Ravi Kant Yadav, Rui Hong Chen, Neha Kumari, Fan Ruiqi, Ashoke Sharon, Nawal Kishore Sahu, Sirish Kumar Ippagunta, Paolo Coghi, Vincent Kam Wai Wong, Sandeep Chaudhary
Summary: A series of spirooxindoles based on nitrostyrene were synthesized and shown to have promising in vitro anticancer activity against human lung and liver cancer cell lines.
Article
Chemistry, Organic
Diksha Bhardwaj, Ruby Singh
Summary: A series of new functionalized analogues of spirooxindole-pyrrolidines have been synthesized via 1,3-dipolar cycloaddition reaction strategy under efficient and eco-friendly conditions. The reaction formed a complex heterocyclic hybrid with multiple stereo centers in one step, showcasing a high regio- and exo-selective manner. Single crystal X-ray diffraction analysis was used to determine the regio-/stereochemistry.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Organic
Asmaa Belabbes, Veronica Selva, Francisco Foubelo, M. De Gracia Retamosa, Jose M. Sansano
Summary: The synthesis of complex spiro{pyrrolidine-3,1'-pyrrolo[3,4-c]pyrrole} skeleton under mild conditions is presented, with the order of addition of a primary amine and two equivalents of corresponding maleimide being crucial for high yields. The mechanism was studied by simple tests, revealing the Michael type addition of the amine onto the maleimide as a key step. Interesting scaffold hybrids were prepared through sequential addition of two different maleimides, and a more intriguing architecture was obtained through a metathesis reaction between allylic residues in the molecule precursor.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yuya Okuyama, Mayu Kidena, Erina Kato, Sayaka Kawano, Koki Ishii, Kenta Maie, Kazuki Miura, Siro Simizu, Takaaki Sato, Noritaka Chida
Summary: A concise synthetic route to peracetylated all-nitrogenated sugars (ANSs) in seven steps from commercially available monosaccharides has been developed. The key to success is the use of sequential Overman rearrangement for ANS synthesis, which shows cytotoxicity against human cancer cell lines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Kazuki Miura, Sayaka Kawano, Takahiro Suto, Takaaki Sato, Noritaka Chida, Siro Simizu
Summary: The study found that madangamine A has strong anti-proliferative activity against human cancer cell lines by inhibiting lysosome function.
BIOORGANIC & MEDICINAL CHEMISTRY
(2021)
Article
Chemistry, Organic
Ryo Minamikawa, Keisuke Fukaya, Akihiro Kobayashi, Yukinori Komiyaa, Shio Yamamoto, Daisuke Urabe, Noritaka Chida, Takaaki Sato
Summary: The asymmetric total synthesis of fasicularin was achieved using a chiral N-alkoxyamide strategy, which changed the reactivity of the amide by incorporating a chiral alkoxy group onto an amide nitrogen. DFT calculations highlighted the importance of pyramidalization of the N-alkoxyamide nitrogen for the aza-spirocyclization reaction. The chiral alkoxy group was also utilized for stereocontrol to establish consecutive stereocenters with high diaste-reoselectivity in the iridium-catalyzed reductive Strecker reaction.
SYNTHESIS-STUTTGART
(2021)
Review
Chemistry, Organic
Takaaki Sato, Takahiro Suto, Yoshiyuki Nagashima, Shori Mukai, Noritaka Chida
Summary: Skipped dienes, found in various biologically active natural products, have relatively undeveloped synthesis methods compared to conjugated dienes due to challenges posed by the sp(3)-hybridized carbon between two olefins. Recent advances in the synthesis of skipped dienes for total synthesis of complex natural products are classified into three categories, focusing on methods to achieve both high stereoselectivity and convergency.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yasukazu Sugiyama, Yasuki Soda, Makoto Yoritate, Hayato Tajima, Yoshito Takahashi, Kana Shibuya, Chisato Ogihara, Takashi Yokoyama, Takeshi Oishi, Takaaki Sato, Noritaka Chida
Summary: In this article, the concise total synthesis of complex alkaloids using a lactam strategy is reported. The strategy enables the assembly of five-membered rings and the synthesis of tricyclic, tetracyclic and pentacyclic stemoamide-type alkaloids. The developed conditions for the lactam-selective nucleophilic reactions are highly versatile and applicable to the synthesis of different types of alkaloids.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2022)
Article
Chemistry, Organic
Shota Iiyama, Keisuke Fukaya, Yu Yamaguchi, Ami Watanabe, Hiroaki Yamamoto, Shota Mochizuki, Ryosuke Saio, Takashi Noguchi, Takeshi Oishi, Takaaki Sato, Noritaka Chida
Summary: The total synthesis of paclitaxel is achieved through a double Rubottom oxidation of the bis(silyl enol ether) derived from a tricarbocyclic diketone, efficiently installing a bridgehead olefin and C-5/C-13 hydroxy groups in one step. Additionally, a novel Ag-promoted oxetane formation method is used to smoothly construct the tetracyclic framework of paclitaxel.
Article
Materials Science, Multidisciplinary
Tomoka Yoshii, Mai Mochida, Kogi Kaizu, Yasuki Soda, Kazuyoshi Kanamori, Kazuki Nakanishi, Takaaki Sato, Hiroaki Imai, Daniel Citterio, Yuki Hiruta
Summary: In this study, an alkali-stable column packing material for reversed-phase preparative high-performance liquid chromatography (HPLC) was developed based on eggshells. The material showed excellent separation and stability in HPLC columns after surface treatment and modification.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Chemistry, Organic
Shona Banjo, Keisuke Nakata, Eiko Nakasuji, Soichiro Yasui, Noritaka Chida, Takaaki Sato
Summary: This study reports a copper-catalyzed electrophilic enamidation starting from alkynes. Hydrozirconation of an alkyne with the Schwartz reagent forms a vinyl zirconium intermediate, which undergoes a copper-catalyzed electrophilic enamidation with dioxazolones. The high functional group tolerance of hydrozirconation enables the use of functionalized alkynes, including esters. The developed conditions are successfully applied to synthesize partial structures found in biologically active natural products.
Article
Chemistry, Organic
Ayaha Kage, Yuya Okuyama, Erina Kato, Tomoe Matagawa, Sayaka Kawano, Siro Simizu, Noritaka Chida, Toshitaka Okamura, Takaaki Sato
Summary: Saponins have various biological and pharmacological activities, with the sugar moiety playing a crucial role in bioactivity. This report focuses on the synthesis and evaluation of saponins with all-nitrogenated sugar (ANS), where all oxygen atoms are replaced with nitrogen atoms. ANS glycosides of OSW-1 derivative, cholesterol, and diosgenin are synthesized through glycosylation with ANS in the presence of TMSOTf. The OSW-1 mimic with ANS exhibits significant cytotoxic activity (IC50 = 7.31 μM) and induces apoptosis.
Article
Chemistry, Organic
Keisuke Fukaya, Takaaki Sato, Noritaka Chida, Daisuke Urabe
Summary: This study provides important insights into the theoretical analysis of complex molecular reactions by investigating the conformations and stereoselectivity of transition states. The findings reveal that the double-bond geometry and stereochemical configuration influence the conformations of the transition states, and that the CH-O hydrogen bond and CH-p interaction play critical roles in asymmetric induction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Crystallography
Takeshi Oishi, Keisuke Fukaya, Takaaki Sato, Noritaka Chida
Summary: The title compound C29H36O9 features a fused tetracyclic system with complex molecular interactions. In the crystal, a three-dimensional network is constructed through hydrogen bonds and interactions, connecting molecules into helical chains along the c-axis direction. There is no valid C-H center dot center dot center dot pi interaction within the structure.
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
(2021)
