Gold(I)-Mediated Cycloisomerization/Cycloaddition Enables Bioinspired Syntheses of Neonectrolides B–E and Analogues

Purgett, Thomas J.; Dyer, Matthew W.; Bickel, Bryce; McNeely, James; Porco, John A.

doi:10.1021/jacs.9b06355

Cited by 8 publications

(7 citation statements)

References 86 publications

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“…a | iso-epicolactone (92) [75,76] , (+)brevianamide Y (93), [77][78][79] (±)-desoxyisobruceol (94) [80][81][82][83] , and (-)-prehalenaquinone (95) [84] are additional examples for molecules that were synthesized in the laboratory prior to their isolation. b | Cases of anticipated natural products that await isolation from natural sources: 8-epi-isoaplydactone (96), [85] dia-angiopterlactone B (97), [86] biyouyanagin C (98), [87] epi-pycnanthuquinone C (99), [88] 8-epi-homodimericin A (100), [89] intricarene side-product (101), [90] protected dia-millingtonine (102) [91] , diaincargranine B aglycone (103) [92] , diastereomer towards neonectrolides (104) [93] , preuisolactone precursor (105) [94] , nuphar alkaloid isomer (106) [95] , side-product towards (+)-norcembrene 5 (107) [96] , monolomaiviticin A (108) [97] , 2-epilankacyclinol (109) [98] , 3,7-epi-massadine (110) [99] , santarubin S (111) [100] , epiguajadial B (112) [101] , Δ 23,24 -perovskone (113) [102] , epi-pungiolide A (114) [103] , and iso-aspergilasine A (115) [104] . This review cannot be comprehensive since it relies mostly on our own experience in the field of biomimetic natural product synthesis and is limited by difficulties in finding diffuse information in the vast chemical literature.…”

Section: Discussionmentioning

confidence: 99%

Natural product anticipation through synthesis

2022

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Natural product synthesis remains one of the most vibrant and intellectually rewarding areas of chemistry, although the justifications for pursuing it have evolved over time. In the early years, the emphasis lay on structure elucidation and confirmation through synthesis, as exemplified by the celebrated studies on cocaine, morphine, strychnine and chlorophyll. This was followed by a phase where the sheer demonstration that highly complex molecules could be recreated in the laboratory in a rational manner was enough to justify the economic expense and intellectual agonies of a synthesis. Since then, syntheses of natural products have served as platforms for the demonstration of elegant strategies, for inventing new methodology "on the fly", or to demonstrate the usefulness and scope of methods established with simpler molecules. We now add another aspect that we find fascinating, viz. "Natural Product Anticipation". In this review, we survey cases where the synthesis of a compound in the laboratory has preceded its isolation from Nature. The focus of our review lies on examples where this anticipation of a natural product has triggered a successful search or where synthesis and isolation occurred independently. Finally, we highlight cases where such a possibility has been suggested but not yet confirmed, inviting further collaborations between synthetic and natural product chemists. The total synthesis of natural products has always been a major factor in the development of organic chemistry. The reasons for pursuing it have evolved as the field has progressed. In its early history, total synthesis mostly served to confirm the constitution and configuration of readily available natural products. With the advent of X-ray crystallography, NMR spectroscopy, and mass spectrometry, this aspect has become less important, although numerous recent cases exist where the structure of a natural product was settled through total synthesis. [1,2] As a consequence, the emphasis has shifted more toward reaction development and the definition of efficient synthetic strategies. In some cases, the desire to achieve a particular transformation has led to the invention of new reactions or reagents that did not exist before. [3] If a total synthesis is sufficiently efficient, it can also be used to deliver a prized natural product on scale that can otherwise only be procured at great expense or by ignoring environmental concerns. [4] Many other motivations for total synthesis exist, ranging from its value as a training ground for medicinal chemists to the satisfaction that comes with solving the sheer intellectual challenge that it represents. [5,6] In this account, we wish to highlight yet another reason to pursue it: Natural Product Anticipation.In the early days of organic synthesis, there must have been many cases where a compound was prepared in the laboratory and considered "synthetic" that was subsequently identified as a natural product. For instance, Gabriel made aminoacetone (1) in 1893 using his eponymous method. [7,8]...

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Section: Discussionmentioning

confidence: 99%

Natural product anticipation through synthesis

2022

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“…122 Consequently, a mechanistic rationale involving the formation of intermediates 156 and 157 was proposed. 121 Secreted by certain symbiotic bacteria like Cytophaga sp. strain YM2-23, Zobellia spp.…”

Section: Formation Of Heterocycles and Spiroketalsmentioning

confidence: 99%

Gold-catalyzed cyclization and cycloaddition in natural product synthesis

Lin,

Liu,

Luo

2024

Nat. Prod. Rep.

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“…Purgett et al. (2019) documented an efficient and scalable total synthesis of neonectrolides B–E 172 a – 172 d via the gold(I)‐catalyzed 167 cycloisomerization/cycloaddition reaction [179] . The researchers initiated the synthetic design from dimethyl 1,3‐acetonedicarboxylate 164 , followed by a Fisher esterification reaction to yield 165 .…”

Section: Gold‐catalyzed Total Synthesis Of Natural Productsmentioning

confidence: 99%

“…Purgett et al (2019) documented an efficient and scalable total synthesis of neonectrolides B-E 172 a-172 d via the gold(I)-catalyzed 167 cycloisomerization/cycloaddition reaction. [179] The researchers initiated the synthetic design from dimethyl 1,3- Additionally, the authors demonstrated that the above strategy, which yielded o-QM substrate, can be successfully applied to the synthesis of corymbiferan lactone E with higher yields and greater selectivity. Thus, the Au(I)-catalyzed alkynol cycloisomerization or the o-QM cycloaddition reaction has enabled the authors to get insight into the diastereoselectivity via the induction of substrate-controlled strategy.…”

Section: Hydroarylation Of Enynol: Neonectrolides B-ementioning

confidence: 99%

Total Synthesis of Natural Products using Gold Catalysis

Dan

Sahu

et al. 2022

Chemistry An Asian Journal

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Gold catalysis is an extremely enthusiastic field of investigation in the catalysis area. The development of alternative, highly inventive, precompetitive techniques based on gold catalysis has paved the way for executing a broad spectrum of chemical transformations from uncomplicated starting materials. The total synthesis of natural products is a complex and more complicated task. An amalgamation of natural product synthesis through goldcatalysis has been a thought-provoking job. The protocol has solved several problems related to the synthesis of numerous complicated natural products. Thus, this review has outlined some of the most notable benchmarks from the last seven years (2015-2021) on gold catalysis and their application in the total synthesis of numerous natural products. The strategy acquired by the authors to accomplish the total synthesis will be elaborately discussed by emphasizing the role of the gold-catalyzed reactions.

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Gold(I)-Mediated Cycloisomerization/Cycloaddition Enables Bioinspired Syntheses of Neonectrolides B–E and Analogues

Cited by 8 publications

References 86 publications

Natural product anticipation through synthesis

Natural product anticipation through synthesis

Gold-catalyzed cyclization and cycloaddition in natural product synthesis

Total Synthesis of Natural Products using Gold Catalysis

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