Total Synthesis of (±)- and (−)-Daphnillonin B

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 10998 - 11004

Published: May 11, 2023

The first total synthesis of (±)- and (-)-daphnillonin B, a daphnicyclidin-type alkaloid with new [7-6-5-7-5-5] A/B/C/D/E/F hexacyclic core, has been achieved. [6-5-7] B/C/D ring system was efficiently diastereoselectively constructed via mild type I intramolecular [5+2] cycloaddition, followed by Grubbs II catalyst-catalyzed radical cyclization. [5-5] fused E/F synthesized diastereoselective Pauson-Khand reaction. Notably, the synthetically challenging core reassembled unique Wagner-Meerwein-type rearrangement from [6-6-5-7-5-5] framework found in calyciphylline A-type Daphniphyllum alkaloids.

Language: Английский

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Enantioselective Total Synthesis of (−)-Daphenylline

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1262 - 1268

Published: Jan. 5, 2024

A concise enantioselective total synthesis of (−)-daphenylline, a hexacyclic Daphniphyllum alkaloid with unique benzene ring, was achieved in 14 steps. The commences two chiral stereocenters, C2 and C18, readily installed via Carreira's Ir/amine dual-catalyzed allylation. allylic bridgehead amine 6 rapidly prepared through Wickens' photoredox-catalyzed hydrocarboxylation olefin CuBr2-catalyzed α-amination ketone. tetracycle 4 formed Pd-catalyzed reductive Heck reaction or, more concisely, by Krische's Rh-catalyzed 1,6-enyne cyclization. In this synthesis, newly reported used twice, Friedel–Crafts acylation thrice.

Language: Английский

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Recent advancements in the chemistry of Diels–Alder reaction for total synthesis of natural products: a comprehensive review (2020–2023)

RSC Advances, Journal Year: 2025, Volume and Issue: 15(6), P. 4496 - 4525

Published: Jan. 1, 2025

This review covers recent advancements in Diels–Alder reaction chemistry for total synthesis of Natural Products (2020–2023) and, where relevant, discusses key structural features and biological activity bioactive natural products.

Language: Английский

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Divergent Total Syntheses of (−)‐Daphnezomines A and B and (+)‐Dapholdhamine B

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: March 30, 2023

The daphnezomine A-type subfamily of Daphniphyllum alkaloids structurally features a unique aza-adamantane core skeleton and anticipates efficient strategies for completing their syntheses to thoroughly investigate biological activities. Herein, divergent total (-)-daphnezomines A B (+)-dapholdhamine have been accomplished in 16-20 steps from known epoxide via rapid construction common intermediate. present work Ti-mediated radical cyclization establish the azabicyclo[3.3.1]nonane ring system, an intramolecular Heck reaction install bridgehead all-carbon quaternary stereocenter, tandem deprotection/reduction/keto amine-carbinolamine tautomerization furnish backbone, NIS-promoted 6-endo-trig aminocyclization assemble backbone.

Language: Английский

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Total Syntheses of Rhodomollins A and B

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(49), P. 27160 - 27166

Published: Nov. 28, 2023

The first and asymmetric total syntheses of rhodomollins A B, two rhodomollane type grayanoids featuring a d-homograyanane carbon skeleton an oxa-bicyclo[3.2.1] core, were accomplished via convergent strategy. Stille coupling lithium-halogen exchange/intramolecular nucleophilic addition to the aldehyde sequence employed assemble enantioenriched fragments. core was achieved through intramolecular SN2 substitution cyclic sulfate 1,2-diols (Williamson ether synthesis). ring oxidation states adjusted by Payne/Meinwald rearrangement subsequent redox transformations.

Language: Английский

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Strategies for constructing seven-membered rings: Applications in natural product synthesis

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(6), P. 109229 - 109229

Published: Oct. 24, 2023

Language: Английский

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Asymmetric total synthesis of polycyclic xanthenes and discovery of a WalK activator active against MRSA

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: July 13, 2024

The development of new antibiotics continues to pose challenges, particularly considering the growing threat multidrug-resistant Staphylococcus aureus. Structurally diverse natural products provide a promising source antibiotics. Herein, we outline concise approach for collective asymmetric total synthesis polycyclic xanthene myrtucommulone D and five related congeners. strategy involves rapid assembly challenging benzopyrano[2,3-a]xanthene core, highly diastereoselective establishment three contiguous stereocenters through retro-hemiketalization/double Michael cascade reaction, Mitsunobu-mediated chiral resolution with high optical purity broad substrate scope. Quantum mechanical calculations insight into stereoselective construction mechanism stereocenters. Additionally, this work leads discovery an antibacterial agent against both drug-sensitive drug-resistant S. This compound operates unique that promotes bacterial autolysis by activating two-component sensory histidine kinase WalK. Our research holds potential future drug development.

Language: Английский

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Molecular Complexity-Inspired Synthetic Strategies toward the Calyciphylline A-Type Daphniphyllum Alkaloids Himalensine A and Daphenylline

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 20, 2024

In this report, we detail two distinct synthetic approaches to calyciphylline A-type

Language: Английский

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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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Recent Progress in the Total Synthesis of Daphniphyllum Alkaloids

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(3), P. 866 - 866

Published: Jan. 1, 2025

Language: Английский

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