Forging the Tetracyclic Core Framework of Daphlongamine B Enabled by a Peripheral Derivation of the Aza-Angular Triquinane Strategy

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 19, 2025

A synthetic route to the highly functionalized tetracyclic core framework of daphlongamine B is described. Key features strategy involve an oxidative dearomatization-induced [4+2] cycloaddition, a di-π-methane rearrangement, and ring-closing metathesis reaction. Our approach enables reliable construction fully elaborated precursor, which, in turn, provides valuable functional handles for further elaboration target molecule.

Language: Английский

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Overcoming (some) rules in synthesis design

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

“Thinking Outside the Box” is most important tool to advance science. The walls of “box” are rules created by previous generations scientists. To overcome such requires courage challenge stability these walls.

Language: Английский

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Synthesis of the AB Ring System of Daphniphyllum Alkaloid Daphniglaucin C

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(3), P. 925 - 925

Published: Jan. 1, 2025

Language: Английский

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Skeletal Editing Strategies Driven by Total Synthesis

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: May 15, 2025

ConspectusSingle-atom skeletal editing strategies that precisely modify the core frameworks of molecules have potential to streamline and accelerate organic synthesis by enabling conceptually simple, but otherwise synthetically challenging, retrosynthetic disconnections. In contrast broader remodeling rearrangement strategies, these methodologies more specifically target single-atom changes with high selectivity, even within complex such as natural products or pharmaceuticals. For past several years, our laboratory has developed methodologies, including ring contractions, expansions, transpositions both saturated unsaturated heterocycles, well other carbon scaffolds. This Account details evolution "skeletal logic" context extensive work on product total synthesis.Early in Sarpong group leveraged metal-mediated C-C bond cleavage situ-generated strained intermediates accomplish syntheses products, icetexane diterpenoids cyathane diterpenes. Continuing focus leveraging through "break-it-to-make-it" we then carvone access a variety terpenoids (including longiborneol sesquiterpenoids, phomactins, xishacorenes) from hydroxylated pinene derivatives. applying this framework alkaloid preparaherquimides lycodine-type alkaloids, recognized nitrogen-containing rings would enable direct conversion between distinct structurally related families. Thus, began developing methods selectively N-heterocycles; led deconstructive fluorination diversification piperidines ultimately recent body direct, modifications (single-atom editing). photomediated enantioselective contractions α-acylated motifs reductive cyclic hydroxylamines. azines (e.g., pyrimidine pyrazole), 15N isotopic labeling azines, phototranspositions indazoles benzimidazoles. To reaction development, cheminformatic analysis heteroaromatic edits served quantitatively inform which transformations most significantly expand accessible chemical space. Apart also reported single-nitrogen insertion amination carbonyl bonds. Ultimately, goal research is develop mild selective can be applied generally. While targeted simplified retrosyntheses logic daphenylline harringtonolide), multiple steps were still required achieve formal desired "edit". As such, continued development truly single-step, mild, reactions edit cores highly remains desirable.

Language: Английский

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Synthetic Study toward Daphnimacropodines

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 4, 2024

Daphnimacropodines A-C are members of a small but structurally distinct subfamily

Language: Английский

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