Generation of azolium dienolates as versatile nucleophilic synthonsvia N-heterocyclic carbene catalysis

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(21), P. 6138 - 6166

Published: Jan. 1, 2021

The recent advances in N -heterocyclic carbene (NHC)-catalyzed generation of azolium dienolates from different precursors and their synthetic applications for the construction various valuable molecules are summarized comprehensively this review.

Language: Английский

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Atroposelective Synthesis of Triaryl α‐Pyranones with 1,2‐Diaxes by N‐Heterocyclic Carbene Organocatalysis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(52)

Published: Oct. 31, 2022

Atropisomers bearing multiple stereogenic axes are of increasing importance to the field material science, pharmaceuticals, and catalysis. However, atroposelective construction multi-axis atropisomers remains rare challenging, due intrinsical difficulties in stereo-control axes. Herein, we demonstrate a single-step new class 1,2-diaxially chiral triaryl α-pyranones by an N-heterocyclic carbene organocatalytic asymmetric [3+3] annulation well-designed alkynyl acylazolium precursors enolizable sterically hindered 2-aryl ketones. The protocol features broad substrate scope (>50 examples), excellent (most cases >20 : 1 dr, up 99.5 0.5 er), potentially useful synthetic applications. success this reaction relies on rational design structurally matched partners careful selection catalytic system. DFT calculations have also been performed discover rationalize origin high stereoselectivity reaction.

Language: Английский

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Chiral Selenide/Achiral Sulfonic Acid Cocatalyzed Atroposelective Sulfenylation of Biaryl Phenols via a Desymmetrization/Kinetic Resolution Sequence

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(7), P. 2943 - 2952

Published: Feb. 10, 2022

Enantioselective synthesis of axially chiral sulfur-containing biaryl derivatives through the electrophilic sulfenylation phenols has been achieved for first time. This catalytic asymmetric system, which involves sequential desymmetrization and kinetic resolution, is enabled by a combination novel 3,3'-disubstituted BINOL-derived selenide catalyst an achiral sulfonic acid. Control experiments computational studies suggest that multiple noncovalent interactions between cocatalysts substrate, especially network hydrogen bond interactions, play crucial role in determining enantioselectivity reactivity.

Language: Английский

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Enantioselective Access to Triaryl-2-pyrones with Monoaxial or Contiguous C–C Diaxes via Oxidative NHC Catalysis

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(4), P. 2565 - 2575

Published: Feb. 6, 2023

We present herein an unprecedented stereoselective synthesis of triaryl-2-pyrones with monoaxial or contiguous diaxes from readily available starting materials. This N-heterocyclic carbene catalysis method adopts atroposelective annulation 2-aryketones ynals under oxidative conditions. The includes the construction one two axes in a single operation, achieves step economy, and affords axially chiral moderate to good yields, high excellent enantioselectivities. DFT calculations relative energies stereoisomers rotational barriers were performed.

Language: Английский

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Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(85), P. 12669 - 12684

Published: Jan. 1, 2023

Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

Language: Английский

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Enantioselective Synthesis of C−O Axially Chiral Diaryl Ethers by NHC‐Catalyzed Atroposelective Desymmetrization**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(52)

Published: Nov. 21, 2023

Axially chiral diaryl ethers, a distinguished class of atropisomers possessing unique dual C-O axis, hold immense potential for diverse research domains. In contrast to the catalytic enantioselective synthesis conventional single axis bearing atropisomers, atroposelective axially ethers containing flexible remains significant challenge. Herein, we demonstrate first N-heterocyclic carbene (NHC)-catalyzed via esterification dialdehyde-containing ethers. Mechanistically, reaction proceeds NHC-catalyzed desymmetrization strategy afford corresponding ether in good yields and high enantioselectivities under mild conditions. The derivatization synthesized product expands utility present access library compounds. temperature dependency preliminary investigations on racemization barrier bonds are also presented.

Language: Английский

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Copper-Catalyzed Asymmetric Functionalization of Vinyl Radicals for the Access to Vinylarene Atropisomers

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(24), P. 13476 - 13483

Published: June 10, 2023

A novel asymmetric radical strategy for the straightforward synthesis of atropisomerically chiral vinyl arenes has been established herein, proceeding through copper-catalyzed atroposelective cyanation/azidation aryl-substituted radicals. Critical to success relay process is capture highly reactive radicals with L*Cu(II) cyanide or azide species. Moreover, these axially vinylarene products can be easily transformed into enriched amides and amines, enantiomerically benzyl nitriles via an axis-to-center chirality transfer process, pure organocatalyst chemo-, diastereo-, enantioselective (4 + 2) cyclization reaction.

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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Diastereo- and atroposelective synthesis of N-arylpyrroles enabled by light-induced phosphoric acid catalysis

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Aug. 9, 2023

The C-N axially chiral N-arylpyrrole motifs are privileged scaffolds in numerous biologically active molecules and natural products, as well ligands/catalysts. Asymmetric synthesis of N-arylpyrroles, however, is still challenging, the simultaneous creation contiguous axial central chirality remains unknown. Herein, a diastereo- atroposelective N-arylpyrroles enabled by light-induced phosphoric acid catalysis has been developed. key transformation one-pot, three-component oxo-diarylation reaction, which simultaneously creates quaternary stereogenic center. A broad range unactivated alkynes were readily employed reaction partner this transformation, products obtained good yields, with excellent enantioselectivities very diastereoselectivities. Notably, skeletons represent interesting structural that could be used ligands catalysts asymmetric catalysis.

Language: Английский

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Carbene‐Catalyzed Intermolecular Dehydrogenative Coupling of Aldehydes with C(sp³)−H Bonds

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

Published: April 5, 2023

The development of catalyst-controlled methods for direct functionalization two distinct C-H bonds represents an appealing approach C-C formations in synthetic chemistry. Herein, we describe organocatalytic straightforward acylation C(sp3 )-H employing readily available aldehyde as "acyl source" involving dehydrogenative coupling aldehydes with ether, amine, or benzylic bonds. developed method affords a broad range ketones under mild conditions. Mechanistically, simple ortho-cyanoiodobenzene is essential the oxidative radical N-heterocyclic carbene catalysis to give ketyl and ) through rarely explored intermolecular hydrogen atom transfer pathway, rendering acylative high efficiency metal- light-free catalytic Moreover, prepared products show promising anti-bacterial activities that shall encourage further investigations on novel agrochemical development.

Language: Английский

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