scholarly journals The Invention of New Methodologies: An Opportunity for Dating Natural Products

Synlett ◽  
2018 ◽  
Vol 29 (16) ◽  
pp. 2108-2116 ◽  
Author(s):  
Louis Fensterbank ◽  
Marion Barbazanges

This Account surveys almost two decades of methodological developments and their straightforward applications to the total synthesis of simple natural products. The main directions covered include radical chemistry and cascades, electrophilic catalysis based on coinage metals, and asymmetric synthesis based on bis(sulfoxides) auxiliaries.1 Introduction2 Radical Cascades2.1 N-Cyanamides2.2 Homolytic Substitution at Sulfur Atom to Give Sultines3 Electrophilic Catalysis Based on Platinum(II) and Gold(I) Complexes4 From Alkylydene Bis(sulfoxides) to Chiral Carboxylic Acids5 Conclusion and Perspectives

2014 ◽  
Vol 10 ◽  
pp. 1228-1232 ◽  
Author(s):  
Jens Schmidt ◽  
Zeinab Khalil ◽  
Robert J Capon ◽  
Christian B W Stark

The heronapyrroles A–C have first been isolated from a marine-derived Streptomyces sp. (CMB-0423) in 2010. Structurally, these natural products feature an unusual nitropyrrole system to which a partially oxidized farnesyl chain is attached. The varying degree of oxidation of the sesquiterpenyl subunit in heronapyrroles A–C provoked the hypothesis that there might exist other hitherto unidentified metabolites. On biosynthetic grounds a mono-tetrahydrofuran-diol named heronapyrrole D appeared a possible candidate. We here describe a short asymmetric synthesis of heronapyrrole D, its detection in cultivations of CMB-0423 and finally the evaluation of its antibacterial activity. We thus demonstrate that biosynthetic considerations and the joint effort of synthetic and natural product chemists can result in the identification of new members of a rare class of natural products.


2021 ◽  
Vol 18 ◽  
Author(s):  
Estibaliz Sansinenea ◽  
Aurelio Ortiz

Background: The total syntheses of complex natural products have evolved to include new methodologies to save time, simplifying the form to achieve these natural compounds. Objective: In this review, we have described the asymmetric synthesis of different natural products and biologically active compounds of the last ten years until the current day. Results: An asymmetric organocatalytic reaction is the key to generate stereoselectively the main structure with the required stereochemistry. Conclusion: Even more remarkable, the organocatalytic cascade reactions, which are carried out with high stereoselectivity, as well as a possible approximation of the organocatalysts activation with substrates are also described.


2021 ◽  
Vol 17 ◽  
pp. 2570-2584
Author(s):  
Scott Benz ◽  
Andrew S Murkin

In the presence of a suitable acid or base, α-hydroxyaldehydes, ketones, and imines can undergo isomerization that features the 1,2-shift of an alkyl or aryl group. In the process, the hydroxy group is converted to a carbonyl and the aldehyde/ketone or imine is converted to an alcohol or amine. Such α-ketol/α-iminol rearrangements are used in a wide variety of synthetic applications including asymmetric synthesis, tandem reactions, and the total synthesis and biosynthesis of natural products. This review explores the use of α-ketol rearrangements in these contexts over the past two decades.


2021 ◽  
Author(s):  
Guang-Jian Mei ◽  
Wai Lean Koay ◽  
Chuan Xiang Alvin Tan ◽  
Yixin Lu

Pyrroloindolines are widely present in natural products. In this review, we summarize state-of-the-art of catalytic asymmetric synthesis of pyrroloindolines, as well as related applications to natural products total synthesis.


2005 ◽  
Vol 77 (7) ◽  
pp. iv
Author(s):  
Tamejiro Hiyama

Organic synthesis has long played a pivotal role in the chemical sciences. It is therefore unsurprising and appropriate that the International Conferences on Organic Synthesis (ICOS) continue to thrive. This series was initiated by IUPAC in 1976 and has since featured biennially as one of the core events of the Union. What is surprising is that 22 years have elapsed since an ICOS event was last hosted by Japan. On that occasion, ICOS-4 was held in 1982 at Shinjuku, Tokyo, and was acclaimed as a great success. The latest event (ICOS-15), in Nagoya, Japan on 1ñ6 August 2004, offered an opportunity to match or surpass the impact of its predecessoróa challenge that was taken up enthusiastically under the leadership of Profs. Minoru Isobe (Nagoya University) and Hisashi Yamamoto (now at the University of Chicago) as Conference co-Chairs. Almost 1000 participants converged on Nagoya from all parts of the world. A noticeably high level of participation by delegates from East Asia in relation to those from North America and Europe attested to the growing capacity of this region to contribute to research at the forefront of this area of the chemical sciences. The scientific program of the Conference embraced all aspects of modern synthetic organic chemistry, inter alia, the invention of selective synthetic methods, asymmetric synthesis, total synthesis of natural products, design and synthesis of artificial agents for pharmaceutical and agricultural uses, and molecular assembly and materials based on molecular function. This topical breadth was also captured in a poster program, which was handsomely supported by no less than 466 displays on every conceivable facet of the subject. Overall, it is evident that organic synthesis has expanded its boundaries increasingly toward biological and material sciences, in response to the new challenges arising from rapid progress in molecular biology and applied physics during recent years.A lecture program comprising 10 plenary and 20 invited presentations, in addition to the Thieme/IUPAC award lecture and two Nagoya medal lectures, contributed to a truly exciting Conference experience, and the 21 speakers who kindly agreed to contribute papers based upon their presentations have made it possible to capture some of the excitement in this issue of Pure and Applied Chemistry. The Nagoya Gold Medallist, J. F. Stoddart, used the occasion to share an absorbing and very personal perspective on molecular assembly and materials, a theme on which M. Fujita also disclosed new insights and developments. The perennial theme of total synthesis of natural products, provided scope for presentation of highly creative accomplishments by S. Ley, J. Cossy, Y. Langlois, R. Pilli, and S. Kozmin on a variety of challenging targets. Such advances in the total synthesis of biologically active natural products having extremely complex structures, often necessitate development of novel synthetic methods, and H. Overkleeft, P. Chiu, V. Nair, T.-P. Loh, S. Martin, T.-Y. Luh, E. Juaristi, and M. Catellani did justice to this theme with presentations on a variety of extremely elegant and sophisticated new developments in methodology, based upon organometallic catalysts and/or reagents. Finally, the broad theme of asymmetric synthesis using organometallic complexes with chiral ligands or chiral organocatalysts was developed in conjunction with combinatorial methodology, which is shown to be highly effective in optimizing catalytic systems. Those who contributed to the topic of asymmetric synthesis are K. Ding, A. Charette, S. H. Kang, A. Berkessel, and K. Maruoka, the recipient of the Nagoya Silver Medal.What is the future of organic synthesis? The invention of unprecedented drugs and materials has enriched and expanded the horizons of the human experience in formerly unimagined ways, and owes much to the ever increasing ingenuity of organic synthesis, and recognition and attainment of new synthetic targets. The impact of organic synthesis on cognate disciplines and on general advancement of science and technology is definitely enormous and will be further strengthened by future challenges and opportunities. Thus, it is hoped that younger generations will be inspired to participate in tapping this rich potential, in the cause of advancing science and contributing to the enrichment of future life. These aspirations may yield incalculable rewards. Such progress will certainly be reflected in the scientific program of the next Conference in the ICOS series, which will take place in Merida, Yucatan, Mexico on 11ñ15 June 2006, under the chairmanship of Dr. Eusebio Juaristi, Instituto Politecnico Nacional, Mexico.Tamejiro HiyamaConference EditorDepartment of Material ChemistryKyoto University, Kyoto, Japan *An issue of reviews and research papers based on lectures presented at the 15th International Conference on Organic Synthesis (ICOS-15), held in Nagoya, Japan, 1-6 August 2004, on the theme of organic synthesis. Other presentations are published in this issue, pp. 1087-1296.


2000 ◽  
Vol 72 (9) ◽  
pp. 1605-1613 ◽  
Author(s):  
Christophe Aïssa ◽  
Bénédicte Delouvrié ◽  
Anne-Lise Dhimane ◽  
Louis Fensterbank ◽  
Max Malacria

This article reviews our contribution in the field of radical synthetic chemistry, focusing on cascades relying on the use of propargylic BMDMS ethers and asymmetric synthesis using enantiopure vinylsulfoxides.


2016 ◽  
Vol 12 ◽  
pp. 1000-1039 ◽  
Author(s):  
Bin Yu ◽  
Hui Xing ◽  
De-Quan Yu ◽  
Hong-Min Liu

Oxindole scaffolds are prevalent in natural products and have been recognized as privileged substructures in new drug discovery. Several oxindole-containing compounds have advanced into clinical trials for the treatment of different diseases. Among these compounds, enantioenriched 3-hydroxyoxindole scaffolds also exist in natural products and have proven to possess promising biological activities. A large number of catalytic asymmetric strategies toward the construction of 3-hydroxyoxindoles based on transition metal catalysis and organocatalysis have been reported in the last decades. Additionally, 3-hydroxyoxindoles as versatile precursors have also been used in the total synthesis of natural products and for constructing structurally novel scaffolds. In this review, we aim to provide an overview about the catalytic asymmetric synthesis of biologically important 3-substituted 3-hydroxyoxindoles and 3-hydroxyoxindole-based further transformations.


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