Elsevier eBooks, Journal Year: 2024, Volume and Issue: unknown
Published: Jan. 1, 2024
Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 755 - 765
Published: April 14, 2025
Asymmetric hydrocyanation of hydrazones, catalyzed by a calcium–BINOL phosphate complex, has been studied for the first time both experimentally and computationally with DFT methods. A full catalytic cycle enantioselective synthesis α-hydrazinonitriles is proposed based on insights gained from calculations. Trimethylsilyl cyanide (TMSCN) used as sacrificial source. We found that isocyanide (rather than cyanide) preferred coordination to calcium during cycle, while active catalyst prefers side-on cyanide. The configuration-determining step via whereas rate-limiting which recovers replaces TMS-bound product catalyst. While our experimental data demonstrate enantioselectivity values high 89% under certain conditions, overall achieved remains modest, mainly due competing pathways Z - E -hydrazone isomers leading opposite enantiomers. results confirm these computational proposals.
Language: Английский
Citations
1
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)
Published: April 29, 2024
Abstract Given the tremendous success of (p‐cymene)Ru II ‐catalyzed C−H activation over past 20 years, community has long been aware that development chiral η 6 ‐benzene (Ben) ligands should be a potent strategy for achieving attractive but incredibly underdeveloped ruthenium(II)‐catalyzed asymmetric activation. However, it rarely achieved due to severe difficulty in developing proper Ben ligands. In particular, designing by connecting benzene fragment framework including rings remained an unsolved challenge until this effort. Here we present novel class axially derived from readily available ( S )‐5,5′,6,6′,7,7′,8,8′‐octahydro‐1,1′‐bi‐2‐naphthol (( )‐H 8 ‐BINOL) 4–8 steps. Notably, when coordinated with ruthenium, such ligand containing three only forms one possible isomeric BenRu complexes. The related catalysts could effectively catalyze N‐sulfonyl ketimines alkynes, affording range spirocyclic sultams up 99 % yield >99 ee. These are expected find broad applications future.
Language: Английский
Citations
5
Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown
Published: March 18, 2025
Chiral phosphoric acids (CPAs) have emerged as highly effective Brønsted acid catalysts in an expanding range of asymmetric transformations, often through novel multifunctional substrate activation modes. Versatile and broadly appealing, these benefit from modular tunable structures, compatibility with additives. Given the unique types noncovalent interactions (NCIs) that can be established between CPAs various reactants─such hydrogen bonding, aromatic interactions, van der Waals forces─it is unsurprising catalyst systems become a promising approach for accessing diverse chiral product outcomes. This review aims to provide in-depth exploration mechanisms by which impart stereoselectivity, positioning NCIs central feature connects broad spectrum catalytic reactions. Spanning literature 2004 2024, it covers nucleophilic additions, radical atroposelective bond formations, highlighting applicability CPA organocatalysis. Special emphasis placed on structural mechanistic features govern CPA-substrate well tools techniques developed enhance our understanding their behavior. In addition emphasizing details stereocontrolling elements individual reactions, we carefully structured this natural progression specifics broader, class-level perspective. Overall, findings underscore critical role catalysis significant contributions advancing synthesis.
Language: Английский
Citations
0
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: April 18, 2025
A novel series of chiral phosphoric acid (CPA) catalysts based on a bioinspired aporphinol scaffold has been developed. The efficacy these CPAs is demonstrated through enantioselective transfer hydrogenation C2-substituted quinolines, achieving excellent enantioselectivities (93-99% enantiomeric excess). They also exhibit catalytic efficiency comparable to that classic acids in the asymmetric Friedel-Crafts reaction and reduction ketone. This work highlights potential aporphinol-based for diverse transformations.
Language: Английский
Citations
0
Molecules, Journal Year: 2024, Volume and Issue: 29(1), P. 239 - 239
Published: Jan. 1, 2024
The two enantiomers of chiral phosphonate 4-phenyldinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepine 4-oxide, O=PPh(BINOL), were synthesized from the proper 1,1'-bi-2-naphtol (BINOL) enantiomer and characterized. structure (
Language: Английский
Citations
2
RSC Advances, Journal Year: 2024, Volume and Issue: 14(2), P. 1134 - 1140
Published: Jan. 1, 2024
Fluorescence recognition for the antimalarial cinchonidine could be achieved efficiently and rapidly through bamboo-like carbon nanotubes based on chiral conjugated H 8 BINOL derivatives.
Language: Английский
Citations
2
Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(6), P. 1412 - 1421
Published: Jan. 23, 2024
Abstract We demonstrate the application of chiral magnesium complexes in an asymmetric carbon‐sulfur bond‐forming reaction. Enantioselective and cost‐effective methodology under mild condition for thia‐Michael addition, utilizing situ generated dinuclear magnesium‐ProPhenol complex, has been developed. The versatility this protocol is demonstrated with a broad range thiol nucleophiles wide selection enones. Enantioenriched β‐ketosulfides are obtained good to excellent yields moderate enantioselectivity. presented catalytic system exhibits tolerance structurally different substrates while maintaining high This observation aligns proposed mechanism, wherein sulfur atom coordinates catalyst close proximity reaction center.
Language: Английский
Citations
2
Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(46)
Published: May 6, 2024
The chemical space of chiral Brønsted acid catalysts is defined by quantity and complexity, reflecting the diverse synthetic challenges confronted innovative molecular designs introduced. Here, we detail how this successful outcome a powerful demonstration benefits utilizing both local structure searches comprehensive understanding catalyst performance for effective efficient exploration properties. In concept article provide an evolutionary overview field summarizing approaches to optimization, resulting structures, functions.
Language: Английский
Citations
2
Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(31)
Published: April 29, 2024
Abstract Given the tremendous success of (p‐cymene)Ru II ‐catalyzed C−H activation over past 20 years, community has long been aware that development chiral η 6 ‐benzene (Ben) ligands should be a potent strategy for achieving attractive but incredibly underdeveloped ruthenium(II)‐catalyzed asymmetric activation. However, it rarely achieved due to severe difficulty in developing proper Ben ligands. In particular, designing by connecting benzene fragment framework including rings remained an unsolved challenge until this effort. Here we present novel class axially derived from readily available ( S )‐5,5′,6,6′,7,7′,8,8′‐octahydro‐1,1′‐bi‐2‐naphthol (( )‐H 8 ‐BINOL) 4–8 steps. Notably, when coordinated with ruthenium, such ligand containing three only forms one possible isomeric BenRu complexes. The related catalysts could effectively catalyze N‐sulfonyl ketimines alkynes, affording range spirocyclic sultams up 99 % yield >99 ee. These are expected find broad applications future.
Language: Английский
Citations
0
Elsevier eBooks, Journal Year: 2024, Volume and Issue: unknown
Published: Jan. 1, 2024
Citations
0