Stereoconfining macrocyclizations in the total synthesis of natural products

2019 ◽  
Vol 36 (11) ◽  
pp. 1546-1575 ◽  
Author(s):  
Kuan Zheng ◽  
Ran Hong
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Natural Product ◽  
The Past

This review covers selected examples of point chirality-forming macrocyclizations in natural product total synthesis in the past three decades.

Synthesis of α-exo-Methylene-γ-butyrolactone: Recent Developments and Applications in Natural Product Synthesis

Synthesis ◽  
2021 ◽  
Author(s):  
Weilong Liu ◽  
Nicolas Winssinger
Keyword(s):  
Natural Products ◽  
Biological Activity ◽  
Total Synthesis ◽  
Natural Product ◽  
Natural Product Synthesis ◽  
Vast Array ◽  
The Past ◽  
New Approaches ◽  
Recent Developments

The α-exo-methylene-γ-butyrolactone moiety is present in a vast array of structurally diverse natural products and is often central to their biological activity. In this review, we summarize new approaches to α-exo-methylene-γ-butyrolactones developed over the past decade as well as their applications in total synthesis.

scholarly journals Heronapyrrole D: A case of co-inspiration of natural product biosynthesis, total synthesis and biodiscovery

2014 ◽  
Vol 10 ◽  
pp. 1228-1232 ◽  
Author(s):  
Jens Schmidt ◽  
Zeinab Khalil ◽  
Robert J Capon ◽  
Christian B W Stark
Keyword(s):  
Antibacterial Activity ◽  
Natural Products ◽  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Natural Product ◽  
Joint Effort ◽  
Natural Product Biosynthesis ◽  
New Members ◽  
Degree Of Oxidation ◽  
Rare Class

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.

scholarly journals Total Synthesis of the Reported Structure of Cahuitamycin A

2020 ◽  
Author(s):  
Justin Shapiro ◽  
Savannah Post ◽  
William Wuest
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Natural Product ◽  
Twelve Step ◽  
Target Compound ◽  
New Family ◽  
Iron Trafficking ◽  
Linear Sequence ◽  
Alternative Structure ◽  
Synthetic Target

In a 2016 screen of natural product extracts a new family of natural products, the cahuitamycins, was discovered and found to inhibit the formation of biofilms in the human pathogen <i>Acinetobacter baumannii</i>. The molecules contain an unusual piperazate residue that raises structure/function and biosynthesis questions and resemble iron-trafficking virulence factors from <i>A. baumannii</i>, suggesting a connection between metal homeostasis and biofilm-mediated pathogenicity. Here we disclose the first total synthesis of the reported structure of cahuitamycin A in a twelve-step longest linear sequence and 18% overall yield. Comparison of spectral data of the authentic natural product and synthetic target compound demonstrate that the reported structure is distinct from the isolated metabolite. Herein, we propose an alternative structure to reconcile our findings with the isolation report, setting the stage for future synthetic and biochemical investigations of an important class of natural products.

scholarly journals Synthetic study of ravidomycin, a hybrid natural product

2000 ◽  
Vol 72 (9) ◽  
pp. 1783-1786 ◽  
Author(s):  
Keisuke Suzuki
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Natural Product ◽  
Amino Sugar ◽  
Antitumor Antibiotics ◽  
Ready Availability ◽  
Silyl Acetals ◽  
Gilvocarcin V ◽  
Absolute Stereochemistry

Strategies and tactics associated with the total synthesis of hybrid natural products are discussed. The target is ravidomycin (2), one of the gilvocarcin-class antitumor antibiotics with an aryl C-glycoside structure. The first total synthesis of 2, which was achieved along similar lines of that of gilvocarcin V (1), served for the determination of the relative as well as the absolute stereochemistry of 2. Also revealed was a limitation of the synthetic scheme so long as the amino sugar congener was concerned. A preliminary result is discussed on the [2+2+2] approach that relies on the ready availability of various benzocyclobutene derivatives via regioselective [2+2] cycloaddition of α-alkoxybenzynes and ketene silyl acetals.

scholarly journals Harnessing the biocatalytic potential of iron- and α-ketoglutarate-dependent dioxygenases in natural product total synthesis

2020 ◽  
Vol 37 (8) ◽  
pp. 1065-1079 ◽  
Author(s):  
Christian R. Zwick ◽  
Hans Renata
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Natural Product ◽  
Oxidative Transformations

This review highlights recent chemoenzymatic syntheses of natural products that feature strategic applications of oxidative transformations with Fe/αKG enzymes.

Recent advances in the synthesis of oxaspirolactones and their application in the total synthesis of related natural products

2019 ◽  
Vol 17 (31) ◽  
pp. 7270-7292 ◽  
Author(s):  
Sagar S. Thorat ◽  
Ravindar Kontham
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Natural Product ◽  
Medicinal Chemistry ◽  
Natural Product Chemistry ◽  
Structural Motifs ◽  
Recent Advances ◽  
Synthetic Molecules ◽  
Product Chemistry

Oxaspirolactones are ubiquitous structural motifs found in natural products and synthetic molecules with a diverse biochemical and physicochemical profile, and represent a valuable target in natural product chemistry and medicinal chemistry.

Ir-Catalyzed reactions in natural product synthesis

2018 ◽  
Vol 5 (1) ◽  
pp. 132-150 ◽  
Author(s):  
Pengquan Chen ◽  
Yuecheng Wu ◽  
Shifa Zhu ◽  
Huanfeng Jiang ◽  
Zhiqiang Ma
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Natural Product ◽  
Natural Product Synthesis ◽  
Catalyzed Reactions

This review highlights the recent applications of Ir-catalyzed reactions in the total synthesis of natural products.

scholarly journals Synthesis of Highly Functionalised Furo[3,4-b]pyrans: Towards the Fungal Metabolite (−)-TAN-2483B

2021 ◽  
Author(s):  
◽  
R.M. Kalpani K. Somarathne
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Natural Product ◽  
Cyclopropane Ring ◽  
Ring Expansion ◽  
Ethyl Esters ◽  
Pyran Ring ◽  
Synthetic Strategy ◽  
Alternative Approach ◽  
Synthetic Approaches

<p>Carbohydrate-derived cyclopropanes combine both the stereochemical wealth of carbohydrates and the reactivity of cyclopropanes. A diverse variety of reaction modes for these cyclopropyl carbohydrates can be harnessed for the synthesis of natural products and other targets.  The natural products (−)-TAN-2483A and (−)-TAN-2483B are fungal secondary metabolites displaying a variety of bioactivities such as inhibition of c-src kinase action and parathyroid hormone-induced bone resorption. This thesis described several synthetic approaches to the natural product (−)-TAN-2483B and analogues of (−)-TAN-2483B employing cyclopropane ring expansion.  The synthetic route to (−)-TAN-2483B began with the readily available substrate D-mannose. The pyran ring unsaturation of the natural product was established by a cyclopropanation-ring expansion sequence. A synthetic strategy via dichlorocyclopropane-based intermediates is described in chapter 2. This being unsuccessful, an alternative approach via 2-fomyl-glycal was developed in chapter 3. The chapter 2 and 3 provided a solid background for the achievement of the analogues synthesis illustrated in chapter 4 via dibromocyclopropane. Lewis acid-mediated alkynylation followed by Pdcatalysed carbonylative lactonisation was successfully utilised in the revelation of the furo[3,4-b]pyran ring skeleton. This route afforded analogues of TAN-2483B; the Z-and E-unsaturated ethyl esters 140 and 141 and hydroxy(−)-TAN-2483B 145. The total synthesis of (−)-TAN-2483B was not achieved due to unforeseen obstacles encountered in the deoxygenation of the side arm of 335 (Chapter 4) into the E-propenyl side arm of (−)-TAN-2483B.</p>

Natural products as modulators of the cyclic-AMP pathway: evaluation and synthesis of lead compounds

2018 ◽  
Vol 16 (35) ◽  
pp. 6372-6390 ◽  
Author(s):  
Saumitra Sengupta ◽  
Goverdhan Mehta
Keyword(s):  
Natural Products ◽  
Cyclic Amp ◽  
Total Synthesis ◽  
Natural Product ◽  
Lead Compounds ◽  
Camp Pathway

Natural product modulators of the cAMP pathway have been evaluated and their total synthesis campaign is described in detail.

scholarly journals Evolution of Pauson-Khand Reaction: Strategic Applications in Total Syntheses of Architecturally Complex Natural Products (2016–2020)

Catalysts ◽  
2020 ◽  
Vol 10 (10) ◽  
pp. 1199
Author(s):  
Sijia Chen ◽  
Chongguo Jiang ◽  
Nan Zheng ◽  
Zhen Yang ◽  
Lili Shi
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Natural Product ◽  
Organic Synthesis ◽  
Total Syntheses

Metal-mediated cyclizations are important transformations in a natural product total synthesis. The Pauson-Khand reaction, particularly powerful for establishing cyclopentenone-containing structures, is distinguished as one of the most attractive annulation processes routinely employed in synthesis campaigns. This review covers Co, Rh, and Pd catalyzed Pauson-Khand reaction and summarizes its strategic applications in total syntheses of structurally complex natural products in the last five years. Additionally, the hetero-Pauson-Khand reaction in the synthesis of heterocycles will also be discussed. Focusing on the panorama of organic synthesis, this review highlights the strategically developed Pauson-Khand reaction in fulfilling total synthetic tasks and its synthetic attractiveness is aimed to be illustrated.

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