A new rearranged and a new seco-ent-kaurane diterpenoids from Isodon parvifolius

Li, Limei; Li, Guo‐You; Xiao, Wei‐Lie; Zhou, Yan; Li, Shenghong; Huang, Sheng‐Xiong; Han, Quan‐Bin; Ding, Li‐Sheng; Lou, Liguang; Sun, Han‐Dong

doi:10.1016/j.tetlet.2006.05.025

Cited by 9 publications

(4 citation statements)

References 19 publications

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“…Isodon diterpenoids, a large family of terpenoid natural products, , are biosynthetically derived from geranylgeranyl-diphosphate (GGPP) via series terpenoid cyclase-catalyzed carbocationic rearrangements. , According to the initial biosynthetic hypothesis, jungermannenone diterpenoids ( 86 ) are derived from ent -kaurane diterpenoids ( 85 ) via two possible carbocationic rearrangement pathways (Scheme A). , During the synthesis of complex Isodon diterpenoids by Lei and co-workers, , initial attempts to convert ent -kaurane-type skeletons into jungermannenone-type skeletons via carbocationic rearrangement on a model substrate were unsuccessful. Interconversion between ent -kauranes and jungermannenones was ultimately achieved via late-stage photochemical rearrangement of the bicyclo[3.2.1]octene moiety (Scheme B).…”

Section: Biosynthetic Implicationsmentioning

confidence: 99%

Late-Stage Diversification of Natural Products

2020

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Late-stage diversification of natural products is an efficient way to generate natural product derivatives for drug discovery and chemical biology. Benefiting from the development of site-selective synthetic methodologies, late-stage diversification of natural products has achieved notable success. This outlook will outline selected examples of novel methodologies for site-selective transformations of reactive functional groups and inert C–H bonds that enable late-stage diversification of complex natural products. Accordingly, late-stage diversification provides an opportunity to rapidly access various derivatives for modifying lead compounds, identifying cellular targets, probing protein–protein interactions, and elucidating natural product biosynthetic relationships.

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Section: Biosynthetic Implicationsmentioning

confidence: 99%

Late-Stage Diversification of Natural Products

2020

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“…Subsequent successive carbocationic cyclization rearrangements generate the three known types of Isodon diterpenoid skeletons (3)(4)(5), each of which features a distinct bicyclo[3.2.1]octene ring system. 19,20 Of note, enzymatic carbocationic rearrangements have been proposed as being responsible for skeletal rearrangements among these Isodon diterpenoid types (Figure 1C): according to the initial biosynthetic hypothesis, 21,22 two possible carbocationic rearrangement pathways have been speculated for the skeletal rearrangement of ent-kaurane diterpenoids into jungermannenone diterpenoids. Such carbocationic rearrangements have long provided great inspiration for synthetic endeavors.…”

Section: The Bigger Picturementioning

confidence: 99%

Photoinduced Skeletal Rearrangements Reveal Radical-Mediated Synthesis of Terpenoids

Hong

Liu

Wang

et al. 2019

Chem

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Protecting-group-free synthesis of (+)-ent-kauradienone and (À)-jungermannenone C has been accomplished through sequential applications of three radical-based reactions, including late-stage photoinduced skeletal rearrangements of bicyclo[3.2.1]octene ring systems. Further investigations on various terpenoids showed good functional-group tolerance and suggest that some terpenoids could also be produced via such photoinduced rearrangements pathways in nature. Our work demonstrates how paying more attention to unconventional radical mechanisms can reveal new chemistries that facilitate the synthesis of complex natural products.

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“…The highly diverse nature of the family makes a divergent synthesis extremely challenging, even for closely related members. Biosynthetically, the jungermannenone natural products have been proposed to derive from ent-kaurane diterpenoids through carbocationic rearrangements [42]. Jungermatrobrunin A (89) [43] bears a highly oxidized scaffold with a unique bicyclo[3.2.1]octene backbone and an unprecedented peroxide bridge (Scheme 7).…”

Section: Total Synthesis Of Dysideanone B (75) and Dysiherbol A (79)mentioning

confidence: 99%

Combining the best of both worlds: radical-based divergent total synthesis

Gennaiou¹,

Kelesidis²,

Kourgiantaki³

et al. 2023

Beilstein J. Org. Chem.

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A mature science, combining the art of the total synthesis of complex natural structures and the practicality of delivering highly diverged lead compounds for biological screening, is the constant aim of the organic chemistry community. Delivering natural lead compounds became easier during the last two decades, with the evolution of green chemistry and the concepts of atom economy and protecting-group-free synthesis dominating the field of total synthesis. In this new era, total synthesis is moving towards natural efficacy by utilizing both the biosynthetic knowledge of divergent synthesis and the latest developments in radical chemistry. This contemporary review highlights recent total syntheses that incorporate the best of both worlds.

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A new rearranged and a new seco-ent-kaurane diterpenoids from Isodon parvifolius

Cited by 9 publications

References 19 publications

Late-Stage Diversification of Natural Products

Late-Stage Diversification of Natural Products

Photoinduced Skeletal Rearrangements Reveal Radical-Mediated Synthesis of Terpenoids

Combining the best of both worlds: radical-based divergent total synthesis

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