Cited by Synthesis of Polycyclic <i>n</i>/5/8 and <i>n</i>/5/5/5 Skeletons Using Rhodium-Catalyzed [5 + 2 + 1] Cycloaddition of Exocyclic-ene-vinylcyclopropanes and Carbon Monoxide

Avoidance of Secondary Carbocations, Unusual Deprotonation, and Nonstatistical Dynamic Effects in the Cyclization Mechanism of Tetraisoquinane DOI

Xiuting Wei,

William DeSnoo, Zining Li

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 29, 2025

The complexity and versatility of terpene cyclization reactions contribute to the wide variety functions properties that terpenoid compounds exhibit in nature. management reactive carbocations over course reaction ultimately arrive at a particular carbon fragment connectivity stereochemistry is no small feat. Bacteria possess TSs generate diverse polycyclic skeletons; however, terpenoids myxobacteria are especially rare. Here, we report first mechanistic study tetraisoquinene biosynthesis from TiqS, diterpene synthase Melittangium boletus. To understand formation unique 5/5/5/5-fused tetraisoquinane skeleton, used isolation structural elucidation nine minor metabolites, site-directed mutagenesis, stable isotope labeling experiments, quantum chemical calculations propose support its mechanism. This reveals new mechanism cyclization, expands our understanding biosynthesis, enables discovery novel natural products myxobacteria.

Language: Английский

Citations

Convergent Total Synthesis of (−)-Calidoustene DOI

Weidong Yao,

Ziqi Liu, Hao Ling

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 29, 2025

The first total synthesis of the sesterterpenoid (-)-calidoustene has been accomplished, featuring a stereoselective Michael/aldol cascade to construct trans-hydrindane backbone, tandem Pummerer/Sakurai cyclization establish bicyclo[3.2.1]octane framework, metallaphotoredox enone coupling followed by MHAT-initiated forge congested central C-ring, and late-stage functionalization via Cu-catalyzed desaturation diimide reduction.

Language: Английский

Citations

Concise Total Syntheses of (−)-Crinipellins A and B Enabled by a Controlled Cargill Rearrangement DOI

Bo Xu, Ziyao Zhang, Dean J. Tantillo

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21250 - 21256

Published: July 25, 2024

Herein, we report concise total syntheses of diterpene natural products (−)-crinipellins A and B with a tetraquinane skeleton, three adjacent all-carbon quaternary centers, multiple oxygenated labile functional groups. Our synthesis features convergent Kozikowski β-alkylation to unite two readily available building blocks all the required carbon atoms, an intramolecular photochemical [2 + 2] cycloaddition install challenging centers 5–6–4–5 tetracyclic controlled Cargill rearrangement rearrange skeleton desired skeleton. These strategically enabling transformations allowed us complete in 12 13 steps, respectively. The results quantum chemical computations revealed that Bronsted acid-catalyzed rearrangements likely involve stepwise paths AlR3-catalyzed concerted path asynchronous alkyl shifting events form product.

Language: Английский

Citations

Spokewise Total Syntheses of Four Erythrina Alkaloids and Telescoped Syntheses of Six Additional Alkaloids DOI

Yue‐Hong Hu,

Zhang‐Yan Gan,

Qin-Tong Li

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 18, 2024

Based on rich sulfur-involving chemical transformations, a novel spokewise synthetic strategy, subclass of the collective strategies, has been developed to concisely synthesize four erythrina alkaloids through single-step transformation from common precursor. Moreover, six additional have also synthesized by subsequent 1-2 steps transformations. The current approaches provide valuable platform for total syntheses and

Language: Английский

Citations

Synthesis of Polycyclic n/5/8 and n/5/5/5 Skeletons Using Rhodium-Catalyzed [5 + 2 + 1] Cycloaddition of Exocyclic-ene-vinylcyclopropanes and Carbon Monoxide DOI

Lu-Ning Wang,

Zhiqiang Huang, Zhi‐Xiang Yu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(10), P. 1732 - 1736

Published: March 7, 2023

A rhodium-catalyzed [5 + 2 1] reaction of exocyclic-ene-vinylcyclopropanes (exo-ene-VCPs) and CO has been realized to access challenging tricyclic n/5/8 skeletons (n = 5, 6, 7), some which are found in natural products. This can be used build tetracyclic n/5/5/5 6), also In addition, 0.2 atm replaced by (CH2O)n as the surrogate achieve with similar efficiency.

Language: Английский

Citations