NiH-Catalyzed Regio- and Enantioselective Hydroalkylation for the Synthesis of β- or γ-Branched Chiral Aromatic N-Heterocycles

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(40), P. 22122 - 22134

Published: Sept. 25, 2023

A nickel hydride-catalyzed regio- and enantioselective hydroalkylation reaction was developed to give access a library of chiral β- or γ-branched aromatic N-heterocycles. This intriguing asymmetric transformation features excellent selectivities, step- atom-economies, generating two kinds products through one synthetic strategy. Furthermore, the possible mechanism extensively investigated using numerous control experiments density functional theory calculations.

Language: Английский

---

One-Pot Construction of β-Selective Quinolines with γ-Quaternary Carbon from Vinylquinolines with Active Ylides via Pd/Sc/Brønsted Acid Co-Catalysis

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(10), P. 6509 - 6517

Published: April 27, 2023

Vinyl-substituted N-heterocycles, as more challenging inert olefins with stable reactivity, have brought about widespread attention in the reaction of aza-Michael addition or reduction coupling reaction. Here, we report a [Pd(η3-C3H5)Cl]2/Sc(OTf)3-catalyzed catalytic process accelerated by Brønsted acids β-selective to yield γ-quaternary carbon from vinyl-substituted quinolines, diazos, and anilines/alcohols one pot. The generation anhydride analogues acid counter anion (OTf–) Lewis promotes activation corresponding nearly quantitative transformation. Both π-cation coordination interactions play pivotal roles vinyl-quinoline substrates activated Sc(OTf)3. control mechanistic evidence DFT calculations presented Pd/Sc/Brønsted co-catalyzed mechanism. triple co-catalytic system provides strategy for vinyl-quinolines linear selectivity containing carbon, developed method shows broad substrate scope varying alkyl/aryl alcohols amines which general rapid quinoline-based diverse library construction.

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

---

α‐Azaaryl carbonyl derivatives in stereodivergent catalytic reactions

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

Published: June 4, 2025

Abstract The catalytic synthesis of chiral azaarenes has become a focal point research due to their signifi`1cant applications across various fields, including medicinal chemistry and materials science. α‐Azaaryl carbonyl compounds, featuring both an electron‐withdrawing C=N moiety within azaarene core functional group, have proven be versatile precursors in the stereochemically intricate azaaryl molecules. In particular, generation α‐azaaryl enolate intermediates, catalyzed by Lewis acids, enabled precise construction α‐stereogenic azaarenes. This review explores recent advances stereodivergent transformations derivatives with array carbon electrophiles, emphasizing efficiency systems involving copper acids combined Ir, Pd, Ni, amine, or Ru catalysts. These strategies offer control over stereochemical outcome, facilitating access all stereoisomers multi‐stereogenic Additionally, we discuss sequence‐dependent approach that allows for controlled stereodivergence reactions derivatives. Through detailed exploration advancements, mechanistic insights, practical applications, this underscores potential unlock new avenues compounds. By presenting diverse expanding opportunities controlling stereochemistry, it fosters further development design structurally complex azaarene‐based frameworks.

Language: Английский

---

Dual Ruthenium-Catalyzed Alkene Isomerization–Hydrogen Auto-Transfer Unlocks Skipped Dienes as Pronucleophiles for Enantioselective Alcohol C–H Allylation

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8576 - 8582

Published: April 5, 2023

The first use of 1,4-pentadiene and 1,5-hexadiene as allylmetal pronucleophiles in regio-, anti-diastereo-, enantioselective carbonyl addition from alcohol proelectrophiles is described. As corroborated by deuterium labeling experiments, primary dehydrogenation delivers a ruthenium hydride that affects alkene isomerization to furnish conjugated diene, followed transfer hydrogenative addition. Hydrometalation appears be assisted the formation fluxional olefin-chelated homoallylic alkylruthenium complex II, which exists equilibrium with its pentacoordinate η1 form enable β-hydride elimination. This effect confers remarkable chemoselectivity: while are competent pronucleophiles, higher 1,n-dienes not, olefinic functional groups products remain intact under conditions 1,4- 1,5-dienes isomerize. A survey halide counterions reveals iodide-bound ruthenium-JOSIPHOS catalysts uniquely effective these processes. method was used prepare previously reported C1–C7 substructure (−)-pironetin 4 vs 12 steps.

Language: Английский

---

The cross-coupling reaction of organoalane reagents with 2-methylthiobenzo[d]thiazolesviaC–S bond cleavage catalyzed by nickel

New Journal of Chemistry, Journal Year: 2023, Volume and Issue: 47(29), P. 14078 - 14094

Published: Jan. 1, 2023

Nickel catalyzed cross-coupling reaction of 2-methylthiobenzo[ d ]thiazole with aryl/alkenyl aluminum to obtain various derivatives 2-(hetero)aryl/2-alkenyl substituted benzo[ ]thiazoles in 31–94% isolated yields.

Language: Английский

---

Copper(I)‐Catalyzed Asymmetric Allylation of Ketones with 2‐Aza‐1,4‐Dienes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 13, 2023

Abstract Catalytic asymmetric allylation of ketones under proton‐transfer conditions is a challenging issue due to the limited pronucleophiles and electrophilic inertness ketones. Herein, copper(I)‐catalyzed with 2‐aza‐1,4‐dienes ( N ‐allyl‐1,1‐diphenylmethanimines) disclosed, which affords series functionalized homoallyl tertiary alcohols in high excellent enantioselectivity. Interestingly, ‐allyl‐1,1‐diphenylmethanimines work as synthetic equivalents propanals. Upon acidic workup, formal β‐addition propanals achieved. An investigation on KIE effect indicates that deprotonation rate‐determining step, generates nucleophilic allyl copper(I) species. Finally, utility present method demonstrated by synthesis R )‐boivinianin A )‐gossonorol.

Language: Английский

---

Harnessing Dpp-Imine as a Powerful Achiral Cocatalyst to Dramatically Increase the Efficiency and Stereoselectivity in a Magnesium-Mediated Oxa-Michael Reaction

JACS Au, Journal Year: 2023, Volume and Issue: 4(1), P. 164 - 176

Published: Dec. 21, 2023

Dpp-imines are classic model substrates for synthetic method studies. Here, we disclose their powerful use as achiral coligands in metal-catalyzed reactions. It is highly interesting to find that the Dpp-imine can not only act ligand create excellent chiral pockets with magnesium complexes but also, more importantly, this coligand dramatically enhance catalytic ability of metal catalyst. The underlying reaction mechanism was extensively explored by conducting a series experiments, including

Language: Английский

---

Polyaromatic Hydrocarbon (PAH)-Based Aza-POPOPs: Synthesis, Photophysical Studies, and Nitroanalyte Sensing Abilities

International Journal of Molecular Sciences, Journal Year: 2023, Volume and Issue: 24(12), P. 10084 - 10084

Published: June 13, 2023

1,4-Bis(5-phenyl-2-oxazolyl)benzene (POPOP) is a common scintillation fluorescent laser dye. In this manuscript, the synthesis of 2-Ar-5-(4-(4-Ar'-1H-1,2,3-triazol-1-yl)phenyl)-1,3,4-oxadiazoles (Ar, Ar' = Ph, naphtalenyl-2, pyrenyl-1, triphenilenyl-2), as PAH-based aza-analogues POPOP, by means Cu-catalyzed click reaction between 2-(4-azidophenyl)-5-Ar-1,3,4-oxadiazole and terminal ethynyl-substituted PAHs reported. An investigation photophysical properties obtained products was carried out, their sensory response to nitroanalytes evaluated. case pyrenyl-1-substituted aza-POPOP, dramatic fluorescence quenching observed.

Language: Английский

---

Copper(I)‐Catalyzed Asymmetric Allylation of Ketones with 2‐Aza‐1,4‐Dienes

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(1)

Published: Nov. 13, 2023

Abstract Catalytic asymmetric allylation of ketones under proton‐transfer conditions is a challenging issue due to the limited pronucleophiles and electrophilic inertness ketones. Herein, copper(I)‐catalyzed with 2‐aza‐1,4‐dienes ( N ‐allyl‐1,1‐diphenylmethanimines) disclosed, which affords series functionalized homoallyl tertiary alcohols in high excellent enantioselectivity. Interestingly, ‐allyl‐1,1‐diphenylmethanimines work as synthetic equivalents propanals. Upon acidic workup, formal β‐addition propanals achieved. An investigation on KIE effect indicates that deprotonation rate‐determining step, generates nucleophilic allyl copper(I) species. Finally, utility present method demonstrated by synthesis R )‐boivinianin A )‐gossonorol.

Language: Английский

---