Synthesis of Tetrahydro-indolones through Rh(III)-Catalyzed [3 + 2] Annulation of Enaminones with Iodonium Ylides

Organic Letters, Journal Year: 2023, Volume and Issue: 25(40), P. 7298 - 7303

Published: Oct. 3, 2023

An unprecedented protocol for a Rh(III)-catalyzed [3 + 2] annulation from simple and readily available enaminones iodonium ylides has been developed. The novel strategy allows access to new class of structurally diverse tetrahydro-indolones with high efficiency broad substrate scope. In addition, this transformation represents the first example selective alkenyl C–H bond functionalization enaminones. Finally, potential applications are demonstrated through gram-scale reaction late-stage modification.

Language: Английский

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Rh(III)-Catalyzed [3 + 2] Annulation/Pinacol Rearrangement Reaction of Enaminones with Iodonium Ylides: Direct Synthesis of 2-Spirocyclo-pyrrol-3-ones

Organic Letters, Journal Year: 2023, Volume and Issue: 25(39), P. 7214 - 7219

Published: Sept. 26, 2023

A novel Rh(III)-catalyzed cascade alkenyl C-H activation/[3 + 2] annulation/pinacol rearrangement reaction of enaminones with iodonium ylides has been developed. This methodology provides a new and straightforward synthetic strategy to afford highly functionalized 2-spirocyclo-pyrrol-3-ones in satisfactory yield from readily available starting materials under mild conditions. Moreover, gram-scale reactions further derivatization experiments are implemented demonstrate the potential utility this developed approach.

Language: Английский

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Construction of Axially Chiral Arylpyrroles via Atroposelective Diyne Cyclization

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: March 30, 2023

Axially chiral biaryls widely exist in natural products and pharmaceuticals are used as ligands catalysts asymmetric synthesis. Compared to the well-established axially 6-membered biaryl skeletons, examples of 5-membered have been quite scarce, mono-substituted 3-arylpyrrole atropisomers not reported. Here, we disclose a copper-catalyzed atroposelective diyne cyclization for construction range arylpyrrole good excellent yields with generally enantioselectivities via oxidation X-H insertion vinyl cations. Importantly, this protocol only represents first synthesis atropisomers, but also constitutes example atropisomer Theoretical calculations further support mechanism cation-involved elucidate origin enantioselectivity.

Language: Английский

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N-Heterocyclic Carbene-Catalyzed Atroposelective Synthesis of N–N Axially Chiral 3-Amino Quinazolinones

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8752 - 8759

Published: June 16, 2023

Although the atroposelective synthesis of biaryls and related compounds bearing axially chiral C–C bonds is well-known, C–N bond-containing relatively less explored, construction N–N has received only scant attention. Demonstrated herein N-heterocyclic carbene (NHC)-catalyzed selective amidation reaction, leading to 3-amino quinazolinones. The NHC-catalyzed reaction quinazolinones containing a free N–H moiety with α,β-unsaturated aldehydes under oxidative conditions furnished atropisomeric quinazolinone derivatives mild broad scope. Preliminary studies on experimental density functional theory-based rotational barrier determination are also presented.

Language: Английский

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Design and Catalytic Asymmetric Synthesis of Furan‐Indole Compounds Bearing both Axial and Central Chirality

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(8)

Published: Dec. 29, 2023

Abstract In the chemistry community, catalytic asymmetric synthesis of furan‐based compounds bearing both axial and central chirality has proven to be a significant but challenging issue owing importance difficulty in constructing such frameworks. this work, we have realized first five‐five‐membered via organocatalytic (2+4) annulation achiral furan‐indoles with 2,3‐indolyldimethanols uncommon regioselectivity. By strategy, furan‐indole were synthesized high yields excellent regio‐, diastereo‐, enantioselectivities. Moreover, theoretical calculations conducted provide an in‐depth understanding reaction pathway, activation mode, origin selectivity.

Language: Английский

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Chiral Acid-Catalyzed Atroposelective Indolization Enables Access to 1,1′-Indole-Pyrroles and Bisindoles Bearing a Chiral N–N Axis

Organic Letters, Journal Year: 2023, Volume and Issue: 25(9), P. 1553 - 1557

Published: March 1, 2023

We present herein a highly atroposelective indolization for the efficient synthesis of 1,1'-biheteroaryls bearing chiral N-N axis. Under cooperative catalysis phosphoric acid and InBr3, reactions between 2,3-diketoesters 1,3-dione-derived enamines resulted in enantioselective construction 1,1'-pyrrole-indoles with up to 92% yield, 94% enantiomeric excess (ee), or bisindoles ee. Derivatizations these compounds diverse functionalized linked axially biheteroaryls have also been demonstrated.

Language: Английский

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Atroposelective Synthesis of N–N Axially Chiral Indoles and Pyrroles via NHC-Catalyzed Diastereoselective (3 + 3) Annulation Strategy

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6965 - 6972

Published: April 18, 2024

The synthesis of N–N axially chiral molecules in the enantiopure form has emerged as an interesting research topic primarily due to significance and intricacy synthesizing these molecules, especially bearing heterocyclic motifs. Herein, we disclose a method for introduction axial chirality along with point center via N-heterocyclic carbene (NHC)-catalyzed atroposelective dihydropyridinone-containing indoles pyrroles. reaction follows (3 + 3) annulation approach by interception indole/pyrrole-derived enamines α,β-unsaturated aldehydes under oxidative NHC catalysis proceeding acylazoliums. indoles/pyrroles were formed mild conditions broad scope high selectivity. In addition, preliminary DFT studies rotational barrier products performed.

Language: Английский

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Atroposelective Synthesis of Axially Chiral Diaryl Ethers by Copper-Catalyzed Enantioselective Alkyne–Azide Cycloaddition

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3475 - 3481

Published: Feb. 21, 2024

Diaryl ethers are important structural motifs widely found in bioactive natural products, ligands, and catalysts. While there a variety of methods available to generate diaryl ethers, progress on the construction axially chiral has been slow. We report herein an atroposelective copper-catalyzed cycloaddition between bisalkynes azides. With indane-fused BOX ligand used, diverse array C–O atropisomers obtained with up 97% yield 99% ee. Control experiments showed that sequential enantioselective desymmetrization–kinetic resolution process is involved, former plays major role. In addition, asymmetric depletion observed for this catalytic synthesis by nonlinear effect studies. By thermal racemization experiments, rotational barrier axis 3aa calculated be 35.9 kcal/mol, which lays foundation its isolation, as well further applications.

Language: Английский

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Atroposelective Synthesis of Diarylamines via Organocatalyzed Electrophilic Amination

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4958 - 4967

Published: March 18, 2024

Axially chiral diarylamine atropisomers represent a distinct category characterized by two contiguous C–N axes, which exhibit significantly lower racemization barrier due to the concerted rotation of both axes. In this work, we introduce an effective method for atroposelective synthesis axially diarylamines through organocatalyzed asymmetric electrophilic amination with azodicarboxylates, afforded variety acyclic secondary in good yields high enantioselectivities. This expands scope catalytic beyond N-aryl quinoid-type atropisomers, enabling without constraining one axis intramolecular hydrogen bonding. Both experimental and computational studies show minimal contribution bonding stabilizing configurations these undergo via

Language: Английский

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Catalytic N-Acylation for Access to N–N Atropisomeric N-Aminoindoles: Choice of Acylation Reagents and Mechanistic Insights

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6926 - 6935

Published: April 18, 2024

The synthesis of N–N axial compounds containing aromatic acyl amides using common acylation reagents remains challenging. We describe a highly atropenantioselective N-aminoindoles axes. A chiral cyclic isothiourea is used as the sole organic catalyst in transformation N-acylation reaction. Aroyl chlorides have been to construct atropisomeric through N-acylation. N-aminoindole products, which bear stereogenic axes, were synthesized with high yields and enantioselectivities. Some enantiopure products exhibited promising antibacterial activities against plant pathogens.

Language: Английский

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