Asymmetric construction of axial and planar chirality with N-heterocyclic carbene (NHC) organocatalysis

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 30, 2024

Language: Английский

---

Enantiopure Turbo Chirality Targets in Tri-Propeller Blades: Design, Asymmetric Synthesis, and Computational Analysis

Molecules, Journal Year: 2025, Volume and Issue: 30(3), P. 603 - 603

Published: Jan. 29, 2025

Enantiopure turbo chirality in small organic molecules, without other chiral elements, is a fascinating topic that has garnered significant interest within the chemical and materials science community. However, further research into application of this concept have been severely limited by lack effective asymmetric tools. To date, only few enantiomers targets isolated, these were obtained through physical separation using HPLC, typically on milligram scales. In work, we report first approach to enantiopure absence elements such as central axial chirality. This demonstrated assembling aromatic phosphine oxides, where three propeller-like groups are anchored P(O) center via axes. Asymmetric induction was successfully carried out sulfonimine auxiliary, with absolute configurations conformations unambiguously determined X-ray diffraction analysis. The resulting frameworks exhibit propellers arranged either clockwise (P,P,P) or counterclockwise (M,M,M) configuration. arrangements, bulkier sides rings oriented toward oxygen atom P=O bond rather than opposite direction. Additionally, orientational configuration controlled auxiliary well, showing one Naph pushed away from group (-CH2-NHSO2-tBu) phenyl ring. Computational studies conducted relative energies for rotational barriers target along axis transition pathway between two enantiomers, meeting our expectations. work expected impact fields chemistry, biomedicine, future.

Language: Английский

---

Copper‐Catalyzed Desymmetric Alkyne–Azide Cycloaddition to Access Axially Chiral Biaryls

European Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Abstract Axially chiral biaryls are an important class of structural units widely used in natural product synthesis, drug design, and as ligands for asymmetric catalysis. Although significant progress has been made the synthesis axially biaryls, some them still limited to narrow substrate ranges, low efficiency, moderate stereocontrol. Herein, we describe a highly efficient route prepare atropisomeric with triazole alkyne modules through desymmetrization prochiral dialkynyl diaryls utilizing cyclobutyl‐bridge box conjunction copper salts. The process mild conditions, good functional‐group tolerance, can obtain wide array valuable biaryl derivatives excellent yields enantioselectivities.

Language: Английский

---

Carbene-catalyzed Phthalide Ether Functionalization for Discovering Chiral Phytovirucides that Specifically Targets Viral Nia Protein to Inhibit Proliferation

Research, Journal Year: 2025, Volume and Issue: 8

Published: Jan. 1, 2025

Plant diseases caused by vegetable viruses are an important threat to global food security, presenting a major challenge for the development of antiviral agrochemicals. Functional proteins plant play crucial role in viral life cycle, and targeted inhibition these has emerged as promising strategy. However, current discovery small molecules is hampered limitations synthetic approaches narrow range targets. Herein, we report practical application organocatalysis serving pesticide that bears unique molecular basis. An N -heterocyclic carbene-modulated reaction first designed asymmetrically functionalize diverse natural phenols with phthalides. Our method capable producing series new phthalidyl ethers under mild conditions good yields, enantioselectivity, functional group tolerance. Among these, compound ( R )- 3w exhibits excellent enantioselectivity-preferred curative activity against potato virus Y (PVY). Mechanistically, it proposed interacts nuclear inclusion body A (Nia) protein PVY at His150 residue. This binding impairs Nia’s function cleavage polyprotein, thereby inhibiting formation replication complex. The study provides insights into advancing protocol facilitate agrochemical discovery, our identified may serve potential lead future research PVY-Nia inhibitors.

Language: Английский

---

Discovery of Staircase Chirality through the Design of Unnatural Amino Acid Derivatives

Research, Journal Year: 2024, Volume and Issue: 7

Published: Jan. 1, 2024

Chirality has garnered significant attention in the scientific community since its discovery by Louis Pasteur over a century ago. It been showing profound impact on chemical, biomedical, and materials sciences. Significant progress made controlling molecular chirality, as evidenced several Nobel Prizes chemistry awarded this area, particularly for advancements asymmetric catalytic synthesis of molecules with central axial chirality. However, exploration new types chirality largely stagnant more than half century, likely due to complexity challenges inherent field. In work, we present novel type chirality—staircase inspired design unnatural amino acid derivatives. The architecture staircase is characterized 2 symmetrical phenyl rings anchored naphthyl pier, asymmetrically displaced influence chiral auxiliaries at their para positions. This unique framework thoroughly using spectroscopic techniques, absolute configuration definitively confirmed x-ray diffraction analysis. Remarkably, one exhibits 4 distinct chirality: central, orientational, turbo, combination that not previously documented literature. Computational studies density functional theory (DFT) calculations were conducted analyze relative energies individual isomers, results are agreement our experimental findings. We believe will open up research frontier catalysis, potential make substantial fields chemistry, medicine, science.

Language: Английский

---

Catalytic Asymmetric Reductive Amination for Axially Chiral Aryl Aldehydes via Desymmetrization/Kinetic Resolution Cascade

Organic Letters, Journal Year: 2024, Volume and Issue: 26(34), P. 7161 - 7165

Published: Aug. 19, 2024

Herein we present an efficient chiral phosphoric-acid-catalyzed atropoenantioselective asymmetric reductive amination of biaryl dialdehydes. The process involves desymmetrization and the following kinetic resolution, with a wide range axially aryl aldehydes obtained high optical purities.

Language: Английский

---

Ni-Catalyzed Desymmetric Radical Cross-Coupling Reaction to Access Axially Chiral Biaryls

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(18), P. 13860 - 13866

Published: Sept. 3, 2024

The synthesis of axially chiral biaryls continues to garner significant attention in the scientific community. In this work, we introduce a Ni-catalyzed desymmetrization strategy for prochiral dibromoarenes, conducted under mild reaction conditions and with good functional group tolerance. This method allows from readily available coupling partners, such as aldehydes, ethers, unactivated alkyl bromides. Moreover, has been successfully applied concise enantioenriched azulene-embedded [7]helicene, promising organic optoelectronics material.

Language: Английский

---