Catalytic Asymmetric Construction of Chiral Polysubstituted 3-Azabicyclo[3.1.1]heptanes by Copper-Catalyzed Stereoselective Formal [4π+2σ] Cycloaddition

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(30), P. 21069 - 21077

Published: July 16, 2024

The direct construction of bioisosteric compounds enriched in C

Language: Английский

---

Chiral Magnesium(II)-Catalyzed Asymmetric Hydroalkylation of Imine-Containing Vinylazaarenes through Conjugate Addition

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

Published: March 29, 2025

The synthesis of chiral azaarenes is great importance for pharmaceutical development. A direct and versatile approach to obtaining such compounds the functionalization imine-containing 2-vinylazaarenes. We have developed a N,N'-dioxide/Mg(II) Lewis acid catalytic system control nucleophilic β-cyclic or acyclic ketone amides/esters overcome strong background reaction, enabling highly efficient enantioselective hydroalkylation 2-vinylazaarenes via conjugate addition. As result, library bearing an all-carbon quaternary stereocenter can be obtained in high yields with good excellent ee values. DFT calculations indicate assistances hydrogen transfer, CH-π interaction between substrate ligand's amide group differentiation.

Language: Английский

---

Catalytic Asymmetric Hydrophosphination of α,β-Unsaturated Aza-heteroarenes

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

Published: April 23, 2025

Here we report a comprehensive investigation of the asymmetric addition diarylphosphorus oxides to wide range α,β-unsaturated pyridines and other N-heterocyclic substrates, catalyzed by commercial chiral phosphoric acid, affording corresponding products in up 99% yield 96% ee. The experimental studies density functional theory calculation suggest possible mechanism role acid control enantioselectivity.

Language: Английский

---

Copper-Catalyzed Regio- and Enantioselective Hydroamination of gem-Difluoroalkenes to Access Chiral Difluoromethyl Amines

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

Published: May 27, 2025

The difluoromethyl group (CF2H) is an important motif in medicinal chemistry. We report the efficient synthesis of a range optically pure α-difluoromethyl amines via copper-catalyzed regio- and enantioselective hydroamination gem-difluoroalkenes. application chiral pyridine-derived ligand inhibits β-F elimination from α-CF2H organocopper intermediate. proposed Cu catalyst promotes production by Cu-H insertion reductive C-N bond using readily available materials. findings this study establish new synthetic strategy to access motifs.

Language: Английский

---

Modular synthesis of polyfunctionalized axial-chiral 2-arylpyridines via cobalt-catalyzed asymmetric [2+2+2] cycloaddition of diynes and nitriles

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111377 - 111377

Published: May 1, 2025

Language: Английский

---

Chiral-at-Tungsten Dioxo Complexes─A Computational Study on Inhibiting Racemization

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 29, 2025

Chiral cis-WO2(acac)2 and cis-WO2(nacnac)2 complexes racemize via four pathways according to DFT calculations at ωB97X-D/6-311+G(2d,f) with LANL2DZ for W inclusion of acetonitrile solvent. Steric congestion by N-Me N-Ph substitution the two nacnac ligands has a substantial geometrical impact raises barriers all pathways. Despite this, even substituted derivatives have same channels racemization. For each these complexes, Dhimba-Muller-Lammertsma (DML) twist is preferred over Conte-Hippler (CH) significantly favored established Bailar (B) Ray-Dutt (RD) twists. The DML barrier WO2(nacnac)2Ph4 large estimated ΔG 25.7 kcal/mol, suggesting it be viable chiral-at-tungsten complex asymmetric catalysis.

Language: Английский

---

Synthesis of Homochiral N‐Heterocyclic Carbene‐Based Nanosheets for Enhanced Asymmetric Catalysis

Advanced Science, Journal Year: 2024, Volume and Issue: 12(2)

Published: Nov. 19, 2024

Abstract Utilizing ultrathin 2D metal–organic framework nanosheets (2D MONs) as supports for incorporating chiral catalysts represents a highly promising avenue in the field of asymmetric catalysis. In this study, four pairs isostructural layers (MOLs) adorned with N ‐Heterocyclic carbene (NHC) groups are successfully synthesized. Notably, obtained bulky ( S )‐1‐Zn crystals can be readily delaminated into MONs consisting 1–2 through an ion intercalation‐assisted exfoliation process. Subsequent catalysis studies revealed that NHC sites effectively activated by proton sponge while maintaining structural integrity subsequent benzoin condensation. Due to their well‐exposed catalytic sites, morphology, and porous structure, exhibited significantly enhanced yield enantioselectivity compared bulk counterparts organic precursors. This research highlights efficient strategy species onto MONs, thereby unlocking immense potential heterogeneous

Language: Английский

---

Synthesis of Some New Chiral Triazole-oxazoline Derivatives

Current Organic Synthesis, Journal Year: 2024, Volume and Issue: 22(1), P. 136 - 142

Published: July 12, 2024

: Some new (S)-2-[1-aryl-5-methyl-1H-1,2,3-triazol-4-yl]-4-benzyl-4,5-dihydro-ox-azoline were synthesized by the reaction of (S)-N-(1-hydroxy-3-phenylpropan-2-yl)-1-aryl-5-methyl-1H-1,2,3-triazole-4-carboxamides which prepared from aromatic amine as start-ing materials, with p-toluenesulfonyl chloride, triethylamine and DMAP. The structures characterized 1H NMR, 13C MS IR. chiral triazole-oxazoline was used a ligand in Diels-Alder asymmetric catalytic between 3-allyl-1,3-ox-azolidin-2-ketone 2-methyl-1,3-butadiene, using PdCl2 catalyst. (S)-3-(4-methylcyclo-hexe-3-ene-1-formyl)-1,3-oxazolidin-2-one obtained. Background: ligands are rarely reported. Objective: aim study to synthsize some (S)-4-benzyl-2-(1-aryl-5-methyl-1H-1,2,3-triazole-4-yl)-4,5-dihydrooxazoline (5a-g). Methods: one-pot methods oriented synthesis adopted. This provides sim-ple effective method for derivatives. Results: (5a-g) cyclization 3-allyl-1,3-oxazolidin-2-ketone 2-methyl-1,3-butadiene catalyzed (S)-4-triazole-oxazoline ligands. Conclusion: (S)-4-benzyl-2-(1-aryl-5-methyl-1H-1,2,3-triazole-4-yl)-4,5-dihydro-oxazoline corresponding N-[(S)-1-hydroxy-3-phenylpropan-2-yl]-1-aryl-5-methyl-1H-1,2,3-triazole-4-formamide, through method. After preliminary evaluation, triazoline-oxazoline ligands, 1,2,3-triazole rings, like pyridine-type materials saved replace one oxazoline ring di-oxazoline reactions.

Language: Английский

---

The influence of Fe2+ on the self-assembly of a bipyridine containing homopolymer: From bowl-shaped nanoparticles to vesicles

European Polymer Journal, Journal Year: 2024, Volume and Issue: unknown, P. 113502 - 113502

Published: Oct. 1, 2024

Language: Английский

---