Dirhodium-Catalyzed Asymmetric Transformations of Alkynes via Carbene Intermediates

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 31, 2025

ConspectusFunctionalization of alkynes is an established cornerstone organic synthesis. While numerous transition metals exhibit promising activities in the transformations via π-insertion or oxidative cyclometalation, Lewis π-acids offer a different approach. By coordinating with through π-bonding, facilitate nucleophilic addition, leading to formation alkenyl metal species. These species can undergo electron rearrangement generate carbenes, which are crucial intermediates for subsequent carbene transfer reactions. This reaction pathway provides versatile route alkyne functionalization, especially asymmetric manner. Although π-acid, gold(I), pioneered this mode, development variants remains challenging due linear coordination gold(I). Therefore, expanding range catalysts beyond gold(I) complexes other would further advances chiral molecule construction and exploration novel modes.In Account, we present concise review multifunctionalization dirhodium-catalyzed transformations, providing modulation strategies substrates plausible mechanisms. In aromatization-driven strategy, furanyl dirhodium generated from enynone, terminated by enantioselective intramolecular C-H insertion, cyclopropanation, aromatic substitution, Büchner reaction, giving dihydroindoles, dihydrobenzofurans, cyclopropane-fused tetrahydroquinolines, fluorenes, cyclohepta[b]benzofurans. The cap-tether strategy was developed study balance reactivity selectivity azo-enyne. gave first catalytic cycloisomerization azo-enyne, affording centrally axially isoindazole derivatives. synergistic activation i.e., EWG C-H···O interaction, introduced achieve enynes, cyclopropane-annulated bicyclic systems enynals. Benefiting these successes, difluoromethyl-substituted enynes were designed proven be effective substrates. With corresponding benzo-1,6-enynes as substrates, biscyclopropanation cascaded cyclopropanation/cyclopropenation achieved using dicarbene equivalents. Additionally, benzo-1,5-enynal vinyl carbene, reacted variety alkenes [2 + 1] cycloaddition, [4 3] formal allylation, spiro fused polycyclic heterocycles. Coupling desymmetrization, successfully diynals, constructing furan-fused dihydropiperidines alkyne-substituted aza-quaternary stereocenter. Notably, analyzing X-ray structures several dirhodium-alkyne π-complexes, together results DFT calculations control experiments, obtained evidence supporting making well-defined paddlewheel-like dirhodium(II) stand out among complexes. We anticipate that our research will significantly advance fields dirhodium, alkyne, chemistry.

Language: Английский

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Recent advances in the construction of axially chiral arylpyrroles

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(9), P. 2480 - 2491

Published: Aug. 9, 2023

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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Enantioselective functionalization of unactivated C(sp3)–H bonds through copper-catalyzed diyne cyclization by kinetic resolution

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 12, 2024

Site- and stereoselective C-H functionalization is highly challenging in the synthetic chemistry community. Although of vinyl cations has been vigorously studied C(sp

Language: Английский

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Asymmetric formal C–C bond insertion into aldehydes via copper-catalyzed diyne cyclization

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

Published: Nov. 3, 2023

The formal C-C bond insertion into aldehydes is an attractive methodology for the assembly of homologated carbonyl compounds. However, homologation has been limited to diazo approach and enantioselective reaction was rarely developed. Herein, we report asymmetric through diyne cyclization strategy. In presence Cu(I)/SaBOX catalyst, this method leads efficient construction versatile axially chiral naphthylpyrroles in moderate excellent yields with good enantioselectivities. This protocol represents a rare example using non-diazo approach. combined experimental computational mechanistic studies reveal mechanism, origin regioselectivity stereoselectivity. Notably, phosphine ligand derived from synthesized skeleton proven be applicable catalysis.

Language: Английский

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Copper-catalysed asymmetric annulation of yne-allylic esters with amines to access axially chiral arylpyrroles

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 10, 2024

The construction of atropisomers with 1,2-diaxes, while maintaining high enantiocontrol, presents a significant challenge due to the dynamic nature steric hindrance at ortho-aryl substituents. Although various catalytic asymmetric methods have been developed for accessing axially chiral arylpyrroles, synthesis arylpyrroles 1,2-diaxes in manner has remained rare. Herein, authors report diverse and C-C C-N axes through copper-catalysed asymmetirc [4 + 1] annulation yne-allylic esters arylamines via remote stereocontrol strategy. This approach provides facile access broad range heterobiaryl (67 examples) excellent enantioselectivities, each bearing one or two C-C/C-N axes, demonstrating its versatility efficiency. utility this methodology is further highlighted by transformation product into phosphine ligand, thioureas use catalysis.

Language: Английский

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Copper-Catalyzed Intermolecular [2 + 2 + 2] Annulation of Diynes with Alkynes: Construction of Carbazoles

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

Published: Jan. 9, 2025

Transition-metal-catalyzed [2 + 2 2] annulation of alkynes is an efficient pathway for the synthesis aromatic compounds. However, most established methods require noble metal catalysts. Herein, we report a copper-catalyzed intermolecular diynes with through vinyl cation intermediates, enabling atom-economical preparation biologically important carbazole skeletons. The reaction shows good regioselectivity in aryl(alkyl)alkynes. Moreover, preliminary results have also been obtained related catalytic atroposelective transformation. This represents rare example non-noble-metal-catalyzed ynamides pathway.

Language: Английский

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Catalytic stereodivergent and simultaneous construction of axial and point chirality

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(12), P. 3308 - 3319

Published: Jan. 1, 2024

An unprecedented ligand-enabled stereodivergent construction of both N–N axial and point chirality in a single step is reported.

Language: Английский

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Asymmetric one-carbon ring expansion of diverse N-heterocycles via copper-catalyzed diyne cyclization

Science Advances, Journal Year: 2024, Volume and Issue: 10(41)

Published: Oct. 9, 2024

One-carbon ring expansion reaction of N-heterocycles has gained particular attention in the past decade because this method allows for conversion readily available into potentially useful complex ring-expanded N-heterocycles, which are inaccessible by traditional methods. However, catalytic asymmetric variant been rarely reported to date. Herein, we disclose an enantioselective one-carbon through chiral copper-catalyzed diyne cyclization, leading practical, atom-economic and divergent assembly array valuable bearing a quaternary stereocenter generally good excellent yields with enantioselectivities (up >99% ee). This protocol represents first example based on alkynes.

Language: Английский

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Organocatalytic intramolecular (4 + 2) annulation of enals with ynamides: atroposelective synthesis of axially chiral 7-aryl indolines

Chemical Science, Journal Year: 2023, Volume and Issue: 14(22), P. 5918 - 5924

Published: Jan. 1, 2023

Catalytic enantioselective transformation of alkynes has become a powerful tool for the synthesis axially chiral molecules. Most these atroposelective reactions rely on transition-metal catalysis, and organocatalytic approaches are largely limited to special which act as precursors Michael acceptors. Herein, we disclose an intramolecular (4 + 2) annulation enals with ynamides. This method allows efficient highly atom-economical preparation various 7-aryl indolines in generally moderate good yields excellent enantioselectivities. Computational studies were carried out elucidate origins regioselectivity enantioselectivity. Furthermore, phosphine ligand derived from synthesized indoline was proven be potentially applicable asymmetric catalysis.

Language: Английский

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