Total Synthesis of (−)‐HM‐3 and (−)‐HM‐4 Using an Asymmetric Gold‐Catalyzed [3,3]‐Sigmatropic Rearrangement of Sulfonium DOI
Weiping Zhou, Arnaud Voituriez

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(17)

Published: March 20, 2023

Abstract The asymmetric total synthesis of two sesquiterpenoids, (−)‐HM‐3 and (−)‐HM‐4, isolated from a phytopathogenic fungus, has been developed using gold‐catalyzed [3,3]‐sigmatropic rearrangement sulfonium as key step. During this transformation, an excellent chirality transfer was observed between the chiral sulfoxide substrate newly formed quaternary stereogenic center with 96 % enantiomeric excess. implementation efficient methodology allowed us to isolate natural products in only 7–8 chemical steps overall yields reaching 12–16 %.

Language: Английский

Catalyst‐Dependent Stereospecific [3,3]‐Sigmatropic Rearrangement of Sulfoxide‐Ynamides: Divergent Synthesis of Chiral Medium‐Sized N,S‐Heterocycles DOI
Guang‐Yu Zhu,

Ji‐Jia Zhou,

Li‐Gao Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(28)

Published: April 27, 2022

Medium-sized N,S-heterocycles have received tremendous interest due to their biological activities and potential medical applications. However, asymmetric synthesis of these compounds are extremely rare. Described herein is a catalyst-dependent [3,3]-sigmatropic rearrangement sulfoxide-ynamides, enabling divergent atom-economic series valuable medium-sized in moderate good yields with broad substrate scope. Importantly, excellent enantioselectivities been achieved via an unprecedented chirality-transfer. Moreover, theoretical calculations employed elucidate the origins stereospecific [3,3]-rearrangement.

Language: Английский

Citations

40

Enantioselective Construction of Quaternary Stereocenters via A Chiral Spiro Phosphoric Acid-Assisted Formal Gold Carbene gem-Dialkylation Reaction DOI
Ke-Wei Chen,

Su Zhou,

Chao Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19261 - 19270

Published: July 1, 2024

Enantioselective construction of all-carbon quaternary stereocenters has attracted much attention over the past few decades. A variety catalytic asymmetric methods have been disclosed based on use presynthesized complex reagents that impart congested steric hindrance to reaction center, which generally produce chiral molecules through forming one C-C bond. The readily available could build two bonds same carbonic center with concomitant assembly remains challenging. Herein, we disclose a alkyne multifunctionalization using gold and spiro phosphoric acid (SPA) for synergistic catalysis. In this method, accessible internal alkynes served as key carbene precursors, followed by

Language: Английский

Citations

11

Synthetic approaches to 1,4-dicarbonyl compounds DOI
Miran Lemmerer, Manuel Schupp, Daniel Kaiser

et al.

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(12), P. 923 - 935

Published: Nov. 7, 2022

Language: Английский

Citations

34

Free Amino Group Transfer via α‐Amination of Native Carbonyls DOI Creative Commons
Minghao Feng, Anthony J. Fernandes, Ana Sirvent

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(28)

Published: April 28, 2023

Abstract We report herein a straightforward transfer of free amino group (NH 2 ) from commercially available nitrogen source to unfunctionalized, native carbonyls (amides and ketones) resulting in direct α‐amination. Primary α‐amino are readily produced under mild conditions, further enabling diverse situ functionalization reactions—including peptide coupling Pictet–Spengler cyclization—that capitalize on the presence unprotected primary amine.

Language: Английский

Citations

20

Collective total synthesis of fusicoccane diterpenoids via Yu [5+2+1] cycloaddition and oxidative Nazarov cyclization DOI Creative Commons

Sujun Xie,

Yuye Chen, Yan Zhang

et al.

Cell Reports Physical Science, Journal Year: 2024, Volume and Issue: 5(3), P. 101855 - 101855

Published: March 1, 2024

The fusicoccane diterpenoids have triggered particular interest from the organic synthesis community in recent years, owing to their promising biological profiles and complex chemical structures. Here, we report collective, asymmetric total syntheses of five diterpenoids, namely fusicoauritone, fusicogigantones A B, fusicogigantepoxide, anadensin. This work features a Yu [5+2+1] cycloaddition that is shown be swift approach access [5,8]-bicyclic ring system an oxidative Nazarov cyclization facilely fabricated critical cyclopentenone moiety via unfunctionalized tertiary divinyl carbinol (TDC) substrate. substrate scope study also revealed general robust transformation capable synthesizing highly substituted cyclopentenones TDCs.

Language: Английский

Citations

7

Total Synthesis of Laurane and Guaiane Sesquiterpenoids via Oxidative Nazarov Reaction DOI
Yuye Chen, Wenqing Chen, Zhiting Zhang

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(11), P. 1267 - 1274

Published: Feb. 19, 2024

Comprehensive Summary As one of the most common structural motifs in natural products, cyclopentenones usually can be fabricated by Nazarov cyclization using divinyl ketones or functionalized tertiary carbinols (TDCs) as substrates. However, straightforward method for transforming unfunctionalized TDCs to their corresponding is currently lacking. Herein, we wish report total syntheses four structurally distinct terpenoids, namely laurane‐type marine sesquiterpenoids isolaurene, debromoaplysin and aplysin, guaiane sesquiterpenoid guaiadienone A, all a novel synthetic method, named oxidative cyclization, key step. This work demonstrated our robust suitable synthesizing various highly substituted cyclopentenones.

Language: Английский

Citations

6

Direct Synthesis of α‐Amino Acid Derivatives by Hydrative Amination of Alkynes DOI Creative Commons
Minghao Feng, Roberto Tinelli, Ricardo Meyrelles

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(1)

Published: Oct. 12, 2022

α-Amino acid derivatives are key components of the molecules life. The synthesis α-amino carbonyl/carboxyl compounds is a contemporary challenge in organic synthesis. Herein, we report practical method for preparation via direct hydrative amination activated alkynes under mild conditions, relying on sulfinamides as nitrogen source. Computational studies suggest that reaction enabled by new type sulfonium [2,3]-sigmatropic rearrangement.

Language: Английский

Citations

18

Gold-Catalyzed [3,3]-Sigmatropic Rearrangement of ortho-Alkynyl-S,S-diarylsulfilimines DOI
Alexandra V. Mackenroth,

Patrick W. Antoni,

Frank Röminger

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(16), P. 2907 - 2912

Published: April 18, 2023

Highly functionalized 5H-pyrrolo[2,3-b]pyrazine cores, carrying a diaryl sulfide moiety at the C-7 position, were obtained from gold-catalyzed reaction using easily accessible ortho-alkynyl-substituted S,S-diarylsulfilimines as intramolecular nitrene transfer reagents for first time. The proceeds under mild conditions, providing excellent yields while tolerating large variety of different substitution patterns. We provide experimental evidence an mechanism, likely including unprecedented amino sulfonium [3,3]-sigmatropic rearrangement.

Language: Английский

Citations

11

Chiral-Controlled Cyclic Chemiluminescence Reactions for the Analysis of Enantiomer Amino Acids DOI
Yanhui Zhong, Yanlong Chen,

Linyuan Chen

et al.

Analytical Chemistry, Journal Year: 2023, Volume and Issue: 95(17), P. 6971 - 6979

Published: April 17, 2023

The similarity and complexity of chiral amino acids (AAs) in complex samples remain a significant challenge their analysis. In this work, the metal-organic framework (MOF)-controlled cyclic chemiluminescence (CCL) reaction is developed utilized analysis enantiomer AAs. MOF d-Co0.75Zn0.25-MOF-74 designed prepared by modifying Co0.75Zn0.25-MOF-74 with d-tartaric acid. bimetallic can not only offer recognize sites but also act as catalyst luminol-H2O2 reaction. Moreover, distinguishable CCL signal be obtained on AAs via control d-Co0.75Zn0.25-MOF-74. amplified difference quantified decay coefficient (k-values) which are calculated from exponential fitting signals. According to simulation results, selective recognition 19 pairs controlled pore size MOF-74 hydrogen-bond interaction acid MOF. Furthermore, k-values used estimate change samples. Consequently, MOF-controlled applied differentiate involved quality monitoring dairy products auxiliary diagnosis, provides new approach for studies potential applications.

Language: Английский

Citations

10

Sustainable electrochemical gold dissolution process based on triboelectric nanogenerator DOI
Ling Huang, Yuxiang Shi,

Yuqing Ren

et al.

Nano Energy, Journal Year: 2023, Volume and Issue: 113, P. 108531 - 108531

Published: May 17, 2023

Language: Английский

Citations

9