Asymmetric dearomative single-atom skeletal editing of indoles and pyrroles

Nature Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

Language: Английский

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Stereoselective Synthesis of Silyl Enol Ethers with Acylsilanes and α,β-Unsaturated Ketones

Organic Letters, Journal Year: 2024, Volume and Issue: 26(28), P. 5911 - 5916

Published: July 8, 2024

Acylsilanes are emerging bench-stable reagents for the generation of electron-rich oxycarbenes that difficult to access with unstable diazo compounds. Herein, we report a siloxycarbene-mediated stereoselective synthesis silyl enol ethers through visible-light-induced intermolecular reactions between acylsilanes and α,β-unsaturated ketones. Both solvent low temperature important success reaction. This approach features atomic economics, exclusive stereocontrol, broad substrate scope. The synthetic potential this methodology is demonstrated by gram-scale reaction various downstream transformations including requiring configuration purity ethers.

Language: Английский

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A Comprehensive Mechanistic Investigation of Sustainable Carbene N-H Insertion Catalyzed by Engineered His-Ligated Heme Proteins

Catalysis Science & Technology, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Engineered heme proteins possess excellent biocatalytic carbene N-H insertion abilities for sustainable synthesis, and most of them have His as the Fe axial ligand. However, information on basic reaction mechanisms is limited, ground states carbenes involved in prior computational mechanistic studies are under debate. A comprehensive quantum chemical pathway study was performed model with a analogue ligand from widely used precursor ethyl diazoacetate aniline substrate. The state this calculated by high-level complete active space self-consistent field (CASSCF) approach, which shows closed-shell singlet that consistent many experimental works. Based this, DFT calculations ten main pathways were compared. Results showed favorable initial formation metal-bound ylide, followed concerted rearrangement/dissociation transition to form free enol, then underwent water-assisted proton transfer process yield final product. This prediction validated via new data using His-ligated myoglobin variants different types carbenes. Overall, first insertions, particularly neutral ligated CASSCF confirmation carbene. results also field. these build solid basis proposed mechanism facilitate future studies.

Language: Английский

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Insight into structure-property relationship of diazo-based carbene-type dyes towards high fixing performance on synthetic fiber

Dyes and Pigments, Journal Year: 2025, Volume and Issue: unknown, P. 112755 - 112755

Published: March 1, 2025

Language: Английский

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P(═O)R₂-Directed Asymmetric Catalytic C–H Olefination Leading to C–N Axially Chiral Targets

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

Published: March 11, 2025

A novel P(═O)R2-directed asymmetric catalytic olefination has been developed, enabling efficient access to carbon–nitrogen axially chiral products with excellent yields (up 92%) and enantioselectivity 99% enantiomeric excess). The synergistic coordination of phosphine oxide functionality l-pGlu-OH the Pd metal center, serving as an directing group ligand, was key success this C–H functionalization system. reaction demonstrated a broad substrate scope, yielding 33 distinct C–N axial products. absolute configuration unambiguously confirmed via X-ray diffraction analysis. Additionally, three representative applications were showcased, involving reduction oxidation produce phosphines related derivatives. plausible cycle mechanism proposed, supported by detailed experimental studies. Aggregates in system identified aggregation-induced polarization experiments.

Language: Английский

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Recent Developments in Enantioselective Silver-Catalyzed Transformations

Organic Preparations and Procedures International, Journal Year: 2025, Volume and Issue: unknown, P. 1 - 95

Published: April 11, 2025

Language: Английский

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Cu-Catalyzed Enantioselective Carbene Insertion into Ge–H and Si–H Bonds Enabled by SPSiBox with a Tunable Chiral Pocket

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

Published: April 28, 2025

Here, we report the Cu-catalyzed asymmetric carbene insertion into both Ge-H and Si-H bonds with α-trifluoromethyl diazo compounds, enabled by a class of newly developed C2-symmetrical bisoxazoline ligands. This protocol provides an efficient method for preparation enantioenriched ogranogermanes organosilanes, featuring broad substrate scope, mild reaction conditions, excellent enantioselectivity, low catalyst loading. The key to tolerance is use SPSiBox ligands bearing flexible tunable chiral pocket. Preliminary mechanistic studies computational unveiled origin induction ligands, mechanism insertion. not only new construction trifluoromethyl-containing molecules but also opens avenue Si- Ge-containing functional molecules.

Language: Английский

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Enantioselective Synthesis of N-Substituted Indoles with α,β-Stereocenters via Sequential Aza-Piancatelli/Cyclization Reactions

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

Published: April 29, 2025

A sequence of catalytic asymmetric aza-Piancatelli rearrangement and Pd-catalyzed cyclization has been developed to construct chiral N-substituted indoles featuring α,β-consecutive stereocenters. This indole framework, bearing α,β-chiral centers, is a prevalent structural motif in natural products biologically active molecules, yet enantioselective methods for its preparation remain scarce. protocol offers efficient access diverse array derivatives with stereocenters, achieving high yields excellent enantioselectivities.

Language: Английский

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Enantioselective N–H Bond Insertion Reaction of Anilines Enabled by Ruthenium and Chiral Phosphoric Acid Cooperative Catalysis

Organic Letters, Journal Year: 2024, Volume and Issue: 26(29), P. 6214 - 6219

Published: July 17, 2024

The enantioselective carbene insertion into N-H bonds of anilines has been realized by cooperative catalysis ruthenium complexes and chiral phosphoric acids, providing the expected α-aryl glycines in moderate to good yields with high enantioselectivity. Typically, slightly modifying reaction conditions, this approach allows bond be effective for both α-alkyl diazoacetates first time enantioselectivity (up 96% 95% ee, respectively).

Language: Английский

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Asymmetric Carbene Insertion into Se‐S Bonds by Synergistic Rh(II)/Guanidine Catalysis Involving Chalcogen‐Bond Assistance

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 2, 2024

The efficient construction of chalcogen-atom-based chiral compounds remains a challenge, despite the importance organoselenium and organosulfur in life materials science. Chalcogen atoms can form net attractive interactions called chalcogen bonds, but it is an undeveloped tool to assist asymmetric catalysis. Herein, we report enantioselective insertion platform install stereogenic center bearing selenyl thiocyano functional groups. Our method operates by synergistic catalysis guanidine achiral dirhodium complex three-component or four-component reaction, through Se-S bond into carbene species, competing successfully with spontaneous racemic process showing high regioselectivity. As elucidated spectroscopic experiments computational studies, unique mechanism involving as well hydrogen bonding was established account for enantiocontrol. stereoselectivity holds broad array selenylthiocyanatopropanoates, which showed excellent anti-inflammatory toward IL-1β low cytotoxicity.

Language: Английский

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