Enantioselective construction of the tricyclic core of curcusones A–D <i>via</i> a cross-electrophile coupling approach

Wright, Austin C.; Stoltz, Brian M.

doi:10.1039/c9sc04127c

Cited by 12 publications

(10 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Noticeably, 5–6‐6‐tricycle unit in the curcusone C 275 was synthesized via Stetter reaction as the key step (Scheme 64). [129] …”

Section: Application Of Stetter Reaction In Total Synthesis Of Naturamentioning

confidence: 99%

“…[128] Stoltz and co-worker in 2019 achieved and reported the short synthesis of the 5-7-6 carbocyclic unit inserted in the curcusone family via Stetter annulation reaction or ring-closing metathesis (RCM) disconnections. [129] The 5-6-6 tricyclic unit 274 to obtain natural curcusones C 275 was accomplished using the reductive cross-coupling reaction of electrophiles 6-bromo-1,4-dioxaspiro [4.4] diglym in the presence of KF and ZnF 2 as co-additive in dimethylformamide (as solvent) in 85 °C. Worthy to mention that bromide 269 was easily synthesized in two steps.…”

Section: Hirota and Co-workers In 2003 Isolated Tetrapetalones Frommentioning

confidence: 99%

“…Moreover, extracts from J. curcas have been extensively examined for their secondary metabolite content [128] . Stoltz and co‐worker in 2019 achieved and reported the short synthesis of the 5–7‐6 carbocyclic unit inserted in the curcusone family via Stetter annulation reaction or ring‐closing metathesis (RCM) disconnections [129] . The 5‐6‐6 tricyclic unit 274 to obtain natural curcusones C 275 was accomplished using the reductive cross‐coupling reaction of electrophiles 6‐bromo‐1,4‐dioxaspiro[4.4]non‐6‐ene 269 and vinyl trifate 270 .…”

Section: Application Of Stetter Reaction In Total Synthesis Of Natura...mentioning

confidence: 99%

“…The extended exposure of the diastereomeric mixture of 273 to strong acid led to a slow olefin migration to afford 274 stereoconvergently, having the required ene-dione scaffold in curcusones AÀ D. Noticeably, 5-6-6-tricycle unit in the curcusone C 275 was synthesized via Stetter reaction as the key step (Scheme 64). [129] Eremophila species are significant to Australian Aboriginal people as drugs. E. sturtii shows anti-inflammatory and/or antimicrobial activities.…”

Section: Hirota and Co-workers In 2003 Isolated Tetrapetalones Frommentioning

confidence: 99%

See 3 more Smart Citations

Recent Advances in Stetter Reaction and Related Chemistry: An update

et al. 2020

View full text Add to dashboard Cite

The Stetter reaction is actually a special CÀ C bond forming reaction through a 1,4-addition reaction in the presence of nucleophilic catalyst. It involves a reaction between aldehydes and Michael acceptors catalyzed by Nheterocyclic carbenes (NHC's) leading to preparation of 1,4dicarbonyl compounds via carbon-carbon bond formation. It offers a powerful approach to access 1,4-dicarbonyl compounds which are significant starting materials and inter-mediates in the synthesis of several heterocyclic systems, and bioactive heterocyclic framework which are present in natural products. In this review we try to underscore the recent advances in Stetter reaction and its applications from 2015 till date. Notably, we focused on the applications of Stetter reaction in the synthesis of various heterocyclic systems and total synthesis of natural products, which have largely been overlooked, previously.

show abstract

“…Noticeably, 5–6‐6‐tricycle unit in the curcusone C 275 was synthesized via Stetter reaction as the key step (Scheme 64). [129] …”

Section: Application Of Stetter Reaction In Total Synthesis Of Naturamentioning

confidence: 99%

Section: Hirota and Co-workers In 2003 Isolated Tetrapetalones Frommentioning

confidence: 99%

Section: Application Of Stetter Reaction In Total Synthesis Of Natura...mentioning

confidence: 99%

Section: Hirota and Co-workers In 2003 Isolated Tetrapetalones Frommentioning

confidence: 99%

See 2 more Smart Citations

Recent Advances in Stetter Reaction and Related Chemistry: An update

et al. 2020

View full text Add to dashboard Cite

show abstract

“…In 2019, Stoltz and co-workers reported their studies toward synthesizing 1a-1d (Fig. 1C) [15][16][17] . Their approach features a divinylcyclopropane-cycloheptadiene rearrangement to forge the 7-membered ring and reached advanced intermediate 14 after 12 steps from 8.…”

mentioning

confidence: 99%

Total Synthesis and Chemoproteomics Connect Curcusone Diterpenes with Oncogenic Protein BRAT1

Dwyer¹,

C²,

Abegg³

et al. 2020

Preprint

View full text Add to dashboard Cite

Natural products are an indispensable source of lifesaving medicine, but natural product-based drug discovery often suffers from scarce natural supply and unknown mode of action. The study and development of anticancer curcusone diterpenes fall into such a dilemma. Meanwhile, many biologically-validated disease targets are considered “undruggable” due to the lack of enzymatic activity and/or predicted small molecule binding sites. The oncogenic BRCA1-associated ATM activator 1 (BRAT1) belongs to such an “undruggable” category. Here, we report our synthetic and chemoproteomics studies of the curcusone diterpenes that culminate in an efficient total synthesis and the identification of BRAT1 as a cellular target. We demonstrate for the first time that BRAT1 can be inhibited by a small molecule (curcusone D), resulting in impaired DNA damage response, reduced cancer cell migration, potentiated activity of the DNA damaging drug etoposide, and other phenotypes similar to BRAT1 knockdown.

show abstract

Metathesis Reactions in Natural Product Fragments and Total Syntheses

et al. 2022

View full text Add to dashboard Cite

The passion of total‐ and fragments syntheses of natural products always remained one of the top priorities among the synthetic chemists worldwide. Due their curiosity toward the complexity of molecules of living nature and their endeavour to imitate them in laboratory; limitless arrays of natural products have been extracted, architecturally‐elucidated, synthesized, and chronicled by utilizing various synthetic methodologies in different fashions. Frequently, the synthesis of complex natural products proceed with inscrutable synthetic challenges, which can be circumvented either by modification of previously developed synthetic methods or by formulating a new one. In this way, a myriad of powerful synthetic reactions have been developed since the genesis of the logic of chemical synthesis. Amongst them, metathesis tactics discovered unexpectedly in the 1950s (Nobel Prize in 2005), have incredibly influenced and changed the landscape of the art of the total and formal synthesis in the last three A. H. Hoveyda, A. R. Zhugralin, me abruptly as compared to other developed transformations or their modified forms. In this particular review article, we envisioned to report a comprehensive detail of the metathetic tools involved in both total and fragments synthesis of natural products in the years 2018 and 2019 along with an overview of 2017.

show abstract

Enantioselective construction of the tricyclic core of curcusones A–D via a cross-electrophile coupling approach

Abstract: Rapid assembly of the carbocyclic core of the curcusone family of natural products is achieved using reductive cross coupling and ring-closing metathesis disconnections.

Cited by 12 publications

References 20 publications

Recent Advances in Stetter Reaction and Related Chemistry: An update

Recent Advances in Stetter Reaction and Related Chemistry: An update

Total Synthesis and Chemoproteomics Connect Curcusone Diterpenes with Oncogenic Protein BRAT1

Metathesis Reactions in Natural Product Fragments and Total Syntheses

Contact Info

Product

Resources

About