The chemistry of recently isolated naturally occurring quinazolinone alkaloids

The present review portrays a concise account of the isolation, bioactivity, and synthesis of bioactive quinazolinone-based natural products for the period 1983-2005 and the recent developments in the area of complex quinazolinone natural products with a special emphasis on new synthetic routes and strategies.     

Natural Product Synthesis at the Interface of Chemistry and Biology

Nature has evolved to produce unique and diverse natural products that possess high target affinity and specificity. Natural products have been the richest sources for novel modulators of biomolecular function. Since the chemical synthesis of urea by Wöhler, organic chemists have been intrigued by natural products, leading to the evolution of the field of natural product synthesis over the past two centuries. Natural product synthesis has enabled natural products to play an essential role in drug discovery and chemical biology. With the introduction of novel, innovative concepts and strategies for synthetic efficiency, natural product synthesis in the 21st century is well poised to address the challenges and complexities faced by natural product chemistry and will remain essential to progress in biomedical sciences.     

[4 1]及[3 2]会聚式四氢呋喃环合成策略在天然产物全合成中的应用进展

四氢呋喃环广泛存在于具有生物活性的天然产物结构当中,立体选择性地构筑四氢呋喃环往往成为这些天然产物全合成研究中的关键。本文归纳了已有全合成报道中的四氢呋喃环成环策略,以实例展示了其中的会聚式合成策略在近年的发展。相比于直线型的分子内关环策略,以[4+1]、[3+2]为代表的会聚式四氢呋喃关环策略往往能够使全合成的整体路线更加简洁高效,更符合全合成研究领域的发展趋势。     

Rapid Generation of Molecular Complexity by Chemical Synthesis: Highly Efficient Total Synthesis of Hexacyclic Alkaloid (−)‐Chaetominine and Its Biosynthetic Implications

The efficiency becomes a key issue in today's natural product total synthesis. While biomimetic synthesis is one of the most elegant strategies to achieve synthetic efficiency and thus to approach the ideal synthesis, most biogenetic pathways are unknown or unconfirmed. In this account, we demonstrate, through the shortest and also the most efficient asymmetric total syntheses of the hexacyclic alkaloid (?)‐chaetominine to date, that on the basis of biogenetic thinking, one can develop quite efficient bio‐inspired total synthesis, which in turn serves to suggest and chemically validate plausible biosynthetic routes for the natural product. The synthetic strategy thus developed is also inspiring for the development of other synthetic methods and efficient total synthesis of other natural products.     

Progress on the total synthesis of natural products in China: From 2006 to 2010

This paper summarizes the progress on the total syntheses of natural products accomplished in mainland China during the period from 2006 to 2010.The overview focuses on the first total synthesis of natural products of contemporary interest including alkaloids,cyclopeptides and cyclic depsipeptides,macrolides,terpenoids and steroids,saponins and glycosides.The development of novel synthetic strategies and methodologies,and application of new selective synthetic methods in the total syntheses of natural products are included as well.     

Recent advances in the total synthesis of cyclopropane-containing natural products

In this tutorial review, recent advances in the synthesis of cyclopropane-containing natural products are discussed, highlighting the application of novel synthetic methodologies and innovative synthetic strategies in the construction of highly functionalized cyclopropanes. The examples showcased herein aim to inspire students and practitioners of organic synthesis to seek further advances in the chemical synthesis of cyclopropanes, both in the context of target-oriented syntheses and method developments.     

Construction of fused polycyclic ethers by strategies involving ring-closing metathesis

Large fused polycyclic ether natural products of marine origin are some of the most complex and formidable synthetic targets found in Nature, and they continue to fascinate and inspire those engaged in target-directed synthesis and the development of new synthetic methods. Novel strategies for the rapid and stereoselective assembly of fused polyethers have been devised in which ring-closing metathesis reactions are used to accomplish cyclic ether construction. Two-directional and iterative ring construction approaches involving ring-closing metathesis are being employed to assemble polyether sequences found in marine natural products such as the ciguatoxins and gambieric acids.     

The cycloaddition strategy for the synthesis of natural products containing carbocyclic seven-membered rings

Highly substituted carbocyclic seven-membered rings are frequently found in natural products and their synthesis represents a significant challenge to the synthetic chemist. Direct intramolecular cyclization of these systems often proves difficult and this fact has catalyzed the development of a variety of strategies based on a convergent intermolecular cycloaddition strategy. This concept article discusses the major cycloaddition approaches utilized to access these types of structures and primarily focuses on examples employed in the synthesis of natural products.     

Assembly of Terpenoid Cores by a Simple,Tunable Strategy

Oxygenated, polycyclic terpenoid natural products have important biological activities. Although total synthesis of such terpenes is widely studied, synthetic strategies that allow for controlled placement of oxygen atoms and other functionality remains a challenge. Herein, we present a simple, scalable, and tunable synthetic strategy to assemble terpenoid‐like polycycloalkanes from cycloalkanones, malononitrile, and allylic electrophiles, abundantly available reagent classes.     

Assembly of Terpenoid Cores by a Simple,Tunable Strategy

Oxygenated, polycyclic terpenoid natural products have important biological activities. Although total synthesis of such terpenes is widely studied, synthetic strategies that allow for controlled placement of oxygen atoms and other functionality remains a challenge. Herein, we present a simple, scalable, and tunable synthetic strategy to assemble terpenoid‐like polycycloalkanes from cycloalkanones, malononitrile, and allylic electrophiles, abundantly available reagent classes.     

Emerging Strategies for the Total Synthesis of Inorganic Nanostructures

New synthetic innovations are rapidly being developed to address the demand for complex, next‐generation nanomaterials with rigorously controlled architectures and interfaces. This Review highlights key strategies for the chemical transformation and stepwise synthesis of multicomponent inorganic nanostructures, with the existing nanoscale transformations categorized into classes of reactions that are related to those used in the synthesis of organic molecules. The application of concepts used in molecular synthesis—including site‐selectivity, regio‐ and chemoselectivity, orthogonal reactivity, coupling reactions, protection/deprotection strategies, and procedures for separation and purification—to nanoscale systems is emphasized. Collectively, the resulting synthetic concept represents an emerging model for the synthesis of complex inorganic nanostructures on the basis of the guiding principles that underpin the multistep total synthesis of complex organic molecules and natural products.     

The Total Synthesis of Isodon Diterpenes

Families of structurally related molecules often provide stimulating targets for organic chemists that are engaged in the development of new methods and strategies for natural product synthesis. While typically focused on specific molecules, these synthetic investigations often lead to generalizable concepts and significant opportunities for learning in a greater sense. Historically well‐investigated families of natural products, such as the prostanoids, indole alkaloids, and macrolide antibiotics, provide ample evidence for the enduring value of these collective activities. In this Minireview, we turn our attention to the polycyclic family of diterpenes isolated from the Isodon genus of plants and provide an account of the recent methods and strategies utilized for their total synthesis.     

核苷二磷酸糖的合成研究进展

核苷二磷酸糖在结构上是由1分子的糖或糖的衍生物和1分子的核苷二磷酸所组成,它是糖基转移酶的供体底物之一。糖基转移酶正被越来越多的应用于制备寡糖、糖缀合物和含糖基天然产物,因此研究核苷二磷酸糖的有效合成方法是很有必要的。本文总结了合成核苷二磷酸糖的各种化学法和酶法。     

Radical transformations for allene synthesis

Allenes are valuable organic molecules that feature unique physical and chemical properties. They are not only often found in natural products, but also act as versatile building blocks for the access of complex molecular targets, such as natural products, pharmaceuticals, and functional materials. Therefore, many remarkable and elegant methodologies have been established for the synthesis of allenes. Recently, more and more methods for radical synthesis of allenes have been developed, clearly emphasizing the associated great synthetic values. In this perspective, we will discuss recent important advances in the synthesis of allenes via radical intermediates by categorizing them into different types of substrates as well as distinct catalytic systems. The mechanistic studies and synthetic challenges will be highlighted.

Recent important advances in the synthesis of allenes via radical strategies are highlighted.     

Synthetic strategies toward the synthesis of polyphenolic natural products: Pauciflorol F and isopaucifloral F: A review

Pauciflorol F and isopaucifloral F are very important polyphenolic natural products and exhibit a variety of biological activities such as antibiotic, anticancer, anti-HIV, antioxidant, antifungal, and anti-inflammatory activities. These important molecules have gained significant attraction of medicinal chemists and several new strategies have been developed toward the synthesis of pauciflorol F and isopaucifloral F. This review article summarizes the major synthetic approaches adopted for the synthesis of these two indanone-based compounds.     

Synthesis of Tetrodotoxin,a Classic but Still Fascinating Natural Product

Tetrodotoxin, a toxic principle of puffer fish intoxication, is one of the most famous marine natural products due to its densely functionalized structure and potent toxicity. Despite its small molecular size (MW 319 g mol^?1), tetrodotoxin has long been well known as a formidable molecule in natural product synthesis. We have devoted more than twenty years to developing synthetic strategies for this molecule, resulting in the preparation of a variety of analogues of tetrodotoxin for biological experiments. This account describes a brief history of tetrodotoxin research and an overview of our synthetic efforts toward tetrodotoxin with the underlying logic and strategy.     

Lessons in Strain and Stability: Enantioselective Synthesis of (+)-[5]-Ladderanoic Acid

The synthesis of structurally complex and highly strained natural products provides unique challenges and unexpected opportunities for the development of new reactions and strategies. Herein, the synthesis of (+)-[5]-ladderanoic acid is reported. En route to the target, unusual and unexpected strain release driven transformations were uncovered. This occurrence required a drastic revision of the synthetic design that ultimately led to the development of a novel stepwise cyclobutane assembly by an allylboration/Zweifel olefination sequence.     

天然产物生物合成:探索大自然合成次生代谢产物的奥秘

天然产物(次生代谢产物)是大自然馈赠给人类的礼物,由于其复杂的骨架结构和良好的药用价值,吸引着化学家们对其进行结构鉴定以及化学合成。尽管人们在天然产物全合成中取得了巨大的成就,但仍然面临着合成路线长、产率低、缺乏选择性等问题。大自然是最伟大的化学家,它利用酶作为催化剂,往往能够高效地合成天然产物。在基因水平上探索大自然合成复杂多样的天然产物的奥秘不仅有助于人们进一步理解和认知有机化学,还为人们开发和利用大自然高效催化化学反应的工具——酶奠定了基础。     

The Total Synthesis of Diquinane-Containing Natural Products

Diquinane or bicyclo[3.3.0]octane is a conspicuous structural unit existing in the carbo-frameworks of a wide range of natural products such as alkaloids and terpenoids. These diquinane-containing molecules not merely exhibit intriguing architectures, but also showcase a broad spectrum of significant bioactivities, which draw widespread attention from the global synthetic community. During the past decade, with an aim to accomplish the total syntheses of such specified cornucopias of natural products, a variety of elegant strategies for construction of the diquinane ring system have been disclosed. In this Minireview, the achievements on this subject in the timeline from 2010 to June 2020 are demonstrated and it is discussed how the diquinane unit is strategically forged in the context of the specific target structure. In addition, impacts of the selected works to the field of natural product total synthesis is highlighted and the particular outlook of diquinane-containing natural product synthesis is provided.     

Lessons in Strain and Stability: Enantioselective Synthesis of (+)‐[5]‐Ladderanoic Acid

The synthesis of structurally complex and highly strained natural products provides unique challenges and unexpected opportunities for the development of new reactions and strategies. Herein, the synthesis of (+)‐[5]‐ladderanoic acid is reported. En route to the target, unusual and unexpected strain release driven transformations were uncovered. This occurrence required a drastic revision of the synthetic design that ultimately led to the development of a novel stepwise cyclobutane assembly by an allylboration/Zweifel olefination sequence.