Total Synthesis of Sculponin U through a Photoinduced Radical Cascade Cyclization

Cao, Wei; Wang, Zhen; Hao, Yan; Wang, Tianli; Fu, Shaomin; Liu, Bo

doi:10.1002/anie.202305516

Cited by 15 publications

(4 citation statements)

References 92 publications

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“…To date, no significant biological activities have been identified for this compound. While several research groups have disclosed reports on the total synthesis of C-20 oxygenated ent -kaurane diterpenoids, the completion of sculponin U ( 77 ) has only been described by our group . Herein, we will highlight our synthesis of sculponin U ( 77 ) through a photoinduced radical cascade cyclization process (Scheme ).…”

Section: Nonmetal-initiated Radical Cyclization In Total Synthesismentioning

confidence: 99%

Total Synthesis with Gram-Scale Radical Process: An Inspiration for Pharmaceutical Industry

Fu,

Liu

2024

Org. Process Res. Dev.

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Radical reactions have emerged as indispensable tools in the synthesis of complex molecules. In this perspective, we will discuss selected total syntheses that make use of radical processes in a scale of at least one gram as the essential transformation, to showcase their potential applicability in the industry related to pharmaceuticals and fine chemicals. The discussion is divided into three main sections: metal-catalyzed hydrogen atom transfer (HAT) cyclization, nonmetal-mediated radical cyclization, and metalcatalyzed reductive cross-coupling reactions. Finally, a summary and outlook of this area are highlighted.

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Section: Nonmetal-initiated Radical Cyclization In Total Synthesismentioning

confidence: 99%

Total Synthesis with Gram-Scale Radical Process: An Inspiration for Pharmaceutical Industry

Fu,

Liu

2024

Org. Process Res. Dev.

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“…In 2023, Liu's group accomplished the total synthesis of sculponin U through a Diels-Alder reaction to form B ring of sculponin U, and a radical cascade cyclization triggered by photoinduced electron transfer (PET) of a silyl enol ether to construct the bicylclo[3.2.1]octane skeleton (C/D rings) (Scheme 9). [13] The total synthesis commenced with dienyne 86, prepared from commercially available 85. Silyl enolization of 86 followed by a thermal Diels-Alder reaction with acrolein, generated an epimeric mixture, which was treated with TEA to yield the thermodynamically stable 87 with 15 : 1 dr value.…”

Section: Total Synthesis Of (�)-And (à )-Sculponin Umentioning

confidence: 99%

Recent Developments in the Syntheses of C‐20‐Oxygenated ent‐Kaurane Diterpenoids

Yue,

Liu

2024

ChemPlusChem

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En t‐kaurane diterpenes are a large group of natural products, with more than 1,000 compounds since their discovery. Due to their excellent biological activities and complex polycyclic structures, these compounds have attracted organic synthesis chemists around the world to be devoted to achieve their total synthesis. At present, the isolated C‐20‐oxygenated ent‐kaurane diterpenes are the most abundant of these natural products, reaching more than 350 in number. However, only total syntheses of 3,20‐epoxy, 7,20‐epoxy and 19,20‐lactone ent‐kaurane diterpenes have been reported. In this review, we elaborate the synthesis of these three types of C‐20 oxygenated ent‐kaurane natural products, discuss these synthetic strategies in detail, and provide good guidance and reference for the synthesis of other C‐20 oxygenated compounds.

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“…Liu and Fu achieved the total synthesis of sculponin U (11), which is isolated from Isodon sculponeatus, a polycyclic C-20oxygenated kaurane diterpenoid featuring a bridge of 7,20lactone-hemiketal functionality (Scheme 3). [17] The key steps contained a radical cascade cyclization to form the cyclohexanone-fused bicyclo[3.2.1]octane skeleton and a Diels-Alder reaction to construct the middle six-membered ring. Although the final sculponin U is racemic, a Ce(OTf) 3 -catalyzed asymmetric Diels-Alder reaction between compound 12 and chiral Nenoyloxazolidinone 2B-1 furnished compound 13 as the major exo diastereomer (92 %, 9.8 : 1 dr).…”

Section: Extension Of Evans' Chiral Auxiliary-based Asymmetric Synthe...mentioning

confidence: 99%

Evans’ Chiral Auxiliary‐Based Asymmetric Synthetic Methodology and Its Modern Extensions

Chen,

Huang

2023

Eur J Org Chem

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Although the asymmetric catalysis has made a spurt of progress, the use of chiral auxiliaries remains crucial in asymmetric synthesis due to both the reliability and versatility of the methods, and the predictability of stereochemistry of the reactions. Up to date, Evans’ chiral non‐racemic oxazolidinone‐based asymmetric synthetic methodology is still widely used in asymmetric synthesis. More importantly, the Evans asymmetric synthetic methodology turned out to be a fruitful source of inspiration for the development of related asymmetric synthetic methodologies. However, although reviews on the application of Evans’ asymmetric synthetic methodology in both organic synthesis and medicinal chemistry continually to appear in the literature, a comprehensive review dedicating to the extensions of Evans’ chiral non‐racemic oxazolidinone‐based asymmetric methodology remains elusive. In this review, we summarize the extensions of the Evans asymmetric methodology, which cover: (1) the modification of the chiral oxazolidinone auxiliaries; (2) the extension of the Evans’ asymmetric aldol reaction from Evans’ syn‐aldol to other diastereomeric aldol adducts; (3) the extension of the asymmetric reaction types; (4) the extension of chiral imide‐type substrates to N‐alkenyl, N‐allenenyl and N‐alkynyl oxazolidinones; (5) the achiral oxazolidinone‐based asymmetric catalysis; (6) the catalytic transformation of Evans’ products; and (7) the straightforward transformations of Evans’ chiral products to other classes of compounds than the chiral carboxylic acids, esters, alcohols, and Weinreb amides.

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Total Synthesis of Sculponin U through a Photoinduced Radical Cascade Cyclization

Cited by 15 publications

References 92 publications

Total Synthesis with Gram-Scale Radical Process: An Inspiration for Pharmaceutical Industry

Total Synthesis with Gram-Scale Radical Process: An Inspiration for Pharmaceutical Industry

Recent Developments in the Syntheses of C‐20‐Oxygenated ent‐Kaurane Diterpenoids

Evans’ Chiral Auxiliary‐Based Asymmetric Synthetic Methodology and Its Modern Extensions

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