Palladium-Catalyzed Ligand-Controlled Switchable Hetero-(5 + 3)/Enantioselective [2σ+2σ] Cycloadditions of Bicyclobutanes with Vinyl Oxiranes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 19621 - 19628

Published: May 13, 2024

For nearly 60 years, significant research efforts have been focused on developing strategies for the cycloaddition of bicyclobutanes (BCBs). However, higher-order and catalytic asymmetric BCBs long-standing formidable challenges. Here, we report Pd-catalyzed ligand-controlled, tunable cycloadditions divergent synthesis bridged bicyclic frameworks. The dppb ligand facilitates formal (5+3) vinyl oxiranes, yielding valuable eight-membered ethers with scaffolds in 100% regioselectivity. Cy-DPEphos promotes selective hetero-[2σ+2σ] to access pharmacologically important 2-oxabicyclo[3.1.1]heptane (O-BCHeps). Furthermore, corresponding O-BCHeps 94–99% ee has achieved using chiral (S)-DTBM-Segphos, representing first cross-dimerization two strained rings. obtained are promising bioisosteres ortho-substituted benzenes.

Language: Английский

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Palladium-catalyzed enantioselective [2σ + 2π] cycloadditions of vinyl-carbonyl-bicyclo[1.1.0]butanes with arylidenemalononitriles

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111072 - 111072

Published: March 1, 2025

Language: Английский

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Palladium-catalysed [2σ + 2π] cycloaddition reactions of bicyclo[1.1.0]butanes with aldehydes

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

Published: Sept. 27, 2024

Language: Английский

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Catalytic Asymmetric Cascade Dearomatization of Indoles via a Photoinduced Pd‐Catalyzed 1,2‐Bisfunctionalization of Butadienes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(26)

Published: April 20, 2024

Photoinduced Pd-catalyzed bisfunctionalization of butadienes with a readily available organic halide and nucleophile represents an emerging attractive method to assemble versatile alkenes bearing various functional groups at the allylic position. However, enantiocontrol and/or diastereocontrol in C-C or C-X bond-formation step have not been solved due open-shell process. Herein, we present cascade asymmetric dearomatization reaction indoles via photoexcited 1,2-biscarbonfunctionalization 1,3-butadienes, wherein control on both electrophile part is achieved for first time photoinduced butadienes. This delivers structurally novel chiral spiroindolenines two contiguous stereogenic centers high diastereomeric ratios (up >20 : 1 dr) good excellent enantiomeric 97 3 er). Experimental computational studies mechanism confirmed radical pathway involving excited-state palladium catalysis. The alignment non-covalent interactions between substrate catalyst were found be essential stereocontrol.

Language: Английский

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Transition-metal-catalyzed enantioselective C–N cross-coupling

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(19), P. 9560 - 9581

Published: Jan. 1, 2024

Chiral amine scaffolds are among the most important building blocks in natural products, drug molecules, and functional materials, which have prompted chemists to focus more on their synthesis. Among accomplishments chiral synthesis, transition-metal-catalyzed enantioselective C-N cross-coupling is considered one of efficient protocols. This approach combines traditional C(sp

Language: Английский

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Palladium-Catalyzed Enantioselective Multicomponent Cross-Coupling of Trisubstituted Olefins

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16892 - 16901

Published: June 6, 2024

The development of a catalytic method for stereogenic carbon center formation holds immense significance in organic synthesis. Transition-metal-catalyzed cross-coupling reaction has been regarded as straightforward and efficient tool stereoselectively forging C–C bond. Nevertheless, the creation acyclic all-carbon quaternary-containing vicinal stereocenters remains notoriously challenging within domain chemistry despite their prominence various bioactive small molecules. Herein, we describe palladium-catalyzed asymmetric multicomponent trisubstituted alkene with aryl diazonium salts arylboronic acids to realize tertiary-quaternary centers high regio-, distereo-, enantioselectivity. Specifically, precise manipulation stereoconfiguration alkenes enables divergent stereoselective reaction, thus allowing facile construction all four enantiomers. Harnessing ligand-swap strategy involving chiral bisoxazoline an achiral fumarate individually accelerates enantioselective migratory insertion reductive elimination step process, supported by density functional theory (DFT) calculations, obviating requirement neighboring directing group internal olefin skeleton.

Language: Английский

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Asymmetric Trapping of Siloxyketenes In Situ Generated from [1,3]-Silyl Migration of α-Ketoacylsilanes: A Visible-Light-Driven Palladium-Catalyzed [4 + 2] Cycloaddition

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 5796 - 5805

Published: March 25, 2025

The transition metal-catalyzed asymmetric [n + 2] cycloaddition reaction with oxy-substituted ketene intermediates remains a synthetic challenge due to the limited availability of suitable precursors. Herein, we report visible-light-driven, palladium-catalyzed [4 vinyl benzoxazinanones siloxyketene intermediates, generating structurally diverse chiral quinolinone derivatives satisfactory diastereo- and enantioselectivities. transient generation siloxyketenes from α-ketoacylsilylanes through visible-light-induced Brook rearrangement is important for success present cycloaddition. 13C-labeling experiments reveal pathway involving [1,3]-silyl migration process. side arm effects BOX ligand silyl steric hindrance α-ketoacylsilanes play crucial roles in stereoselectivity control, theoretical calculations provide insights into stereochemical outcome reaction.

Language: Английский

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Sustainable click reactions: Use of greener reaction media in the synthesis of 1,2,3-triazoles

Tetrahedron, Journal Year: 2024, Volume and Issue: 157, P. 133964 - 133964

Published: March 31, 2024

Language: Английский

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Enantioselective Synthesis of P-Chiral Phosphine Oxides Bearing an All-Carbon Quaternary Stereogenic Center via Palladium-Catalyzed Domino Heck–Suzuki Reaction

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 14762 - 14768

Published: Sept. 20, 2024

Language: Английский

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Pd/Cu-Cocatalyzed Enantio- and Diastereodivergent Wacker-Type Dicarbofunctionalization of Unactivated Alkenes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(38), P. 26121 - 26130

Published: Aug. 5, 2024

The Wacker and Wacker-type reactions are some of the most fundamental powerful transformations in organic chemistry for their ability to efficiently produce valuable chemicals. Remarkable progress has been achieved asymmetric oxy/aza-Wacker-type reactions; however, dicarbofunctionalization remains underdeveloped, especially concurrent construction two stereocenters. Herein, we report a Pd/Cu-cocatalyzed enantio- diastereodivergent alkene-tethered aryl triflates with imino esters. A series 2-indanyl motifs bearing adjacent carbon stereocenters could be easily synthesized moderate excellent yields good diastereo- enantioselectivities (up >20:1 dr >99% ee). Density functional theory calculations revealed that origin diastereoselectivity this Pd/Cu synergistic catalytic system is jointly determined by both intermolecular anti-carbopalladation alkenes reductive elimination processes, accordance Curtin–Hammett principle.

Language: Английский

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