4-Vinylbenzodioxinones as a new type of precursor for palladium-catalyzed (4+3) cycloaddition of azomethine imines

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(11), P. 1436 - 1439

Published: Jan. 1, 2024

Benzo-fused cyclic carbonates were designed and synthesized as a novel type of precursor π-allylpalladium zwitterionic intermediates.

Language: Английский

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Isolable Spirocyclic Silylone: π-Delocalized Spiro[3.3]heptasila-2,6-diylidone

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(21), P. 14410 - 14415

Published: May 16, 2024

Strained cyclic tetrylones are important synthons due to various synthetic applications. Connecting two tetrylone rings through a single shared quaternary group 14 element atom form spirocyclic molecule has been unexplored both theoretically and experimentally. The formation of motif challenge. In contrast, the reaction amidinato disilicon(I) 1, (Me3P)2SiCl4, KC8 afforded π-delocalized spiro[3.3]heptasila-2,6-diylidone2 tetrasilacyclobutadiene byproducts 3 4. Compound 2 is smallest derivative, which composed σ-type lone pair delocalized π bond in each all-silicon ring. electronic property supported by its coordination with W(CO)5 moiety.

Language: Английский

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Recent advances in ligand-enabled palladium-catalyzed divergent synthesis

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 22(1), P. 37 - 54

Published: Nov. 27, 2023

Developing efficient and straightforward strategies to rapidly construct structurally distinct diverse organic molecules is one of the most fundamental tasks in synthesis, drug discovery materials science. In recent years, divergent synthesis functional from same starting has attracted significant attention been recognized as an powerful strategy. To achieve this objective, proper adjustment reaction conditions, such catalysts, solvents, ligands, etc., required. review, we summarized efforts chemo-, regio- stereodivergent reactions involving acyclic cyclic systems catalyzed by palladium complexes. Meanwhile, types, including carbonylative reactions, coupling cycloaddition well probable mechanism have also highlighted detail.

Language: Английский

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Nickel-catalyzed acylzincation of allenes with organozincs and CO

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

Published: Oct. 31, 2023

Transition metal-catalyzed carbonylative reaction with CO gas are among the central task in organic synthesis, enabling construction of highly valuable carbonyl compound. Here, we show an earth-abundant nickel-catalyzed three-component tandem acylzincation/cyclization sequence allene and alkylzinc reagent 1 atm under mild conditions. This protocol is featured by broad functional group tolerance high selectivity, providing a rapid convenient synthetic method for diverse fully substituted benzotropone derivatives. Mechanistic studies reveal that installation cyano tethered to moiety enables regio- stereoselectivity this acylzincation allene, allowing selective formation three consecutive C-C bonds efficient manner.

Language: Английский

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Access to Complex Scaffolds Through [2 + 2] Cycloadditions of Strained Cyclic Allenes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 15420 - 15427

Published: May 20, 2024

We report the strain-induced [2 + 2] cycloadditions of cyclic allenes for assembly highly substituted cyclobutanes. By judicious choice trapping agent, complex scaffolds bearing heteroatoms, fused rings, contiguous stereocenters, spirocycles, and quaternary centers are ultimately accessible. Moreover, we show that resulting cycloadducts can undergo thermal isomerization. This study provides an alternative strategy to photochemical accessing functionalized cyclobutanes, while validating use underexplored strained intermediates architectures.

Language: Английский

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Substrate-Controlled [8 + 3] Cycloaddition of Tropsulfimides and Tropones with Zwitterionic Allenyl Palladium Species Derived from Vinylidenecyclopropane-diesters

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 4, 2024

A palladium-catalyzed regioselective [8 + 3] cycloaddition of tropsulfimides and tropones with vinylidenecyclopropane-diesters (VDCP-diesters) has been disclosed in this paper, affording decahydro-1

Language: Английский

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Geometric distortion as an enabling tool for organic synthesis

Nature Synthesis, Journal Year: 2025, Volume and Issue: 4(4), P. 421 - 431

Published: April 9, 2025

Language: Английский

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A Rh^II-Catalyzed [4 + 3]-Cycloaddition via the Stereoselective Cyclopropanation of Vinyl Allenes En Route to Oxepino[b]indoles and Subsequent Elaboration to Spirooxindole Frameworks

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

Published: May 1, 2025

Oxepino[b]indoles were obtained in good to excellent yields employing a [4 + 3]-cycloaddition initiated by stereo- and regioselective, RhII-catalyzed cyclopropanation between vinyl allene diazooxindole afford an intermediate cyclopropyl that engaged the oxindole carbonyl spontaneous hetero-[3,3]-rearrangement. A survey of functional group tolerance revealed diverse array substrates amenable oxepino[b]indole formation. In addition intriguing architecture cycloadducts, exposure either Brønsted acid or base enables assembly functionalized spirroxindoles via unusual conversion 5-7 fused ring system 5-5 spirocycle.

Language: Английский

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Cyclic Allene Approach to the Manzamine Alkaloid Keramaphidin B

Organic Letters, Journal Year: 2023, Volume and Issue: 25(30), P. 5553 - 5557

Published: June 30, 2023

We report an approach to the core of manzamine alkaloid keramaphidin B that relies on strain-promoted cycloaddition azacyclic allene with a pyrone trapping partner. The is tolerant nitrile and primary amide functional groups can be complemented subsequent retro-Diels–Alder step. These efforts demonstrate strained cyclic allenes used build significant structural complexity should encourage further studies these fleeting intermediates.

Language: Английский

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Asymmetric cascades of the π-allyl complex: a journey from transition-metal catalysis to metallaphotocatalysis

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(76), P. 11298 - 11319

Published: Jan. 1, 2023

The enantioselective catalytic cascade involving Tsuji-Trost allylation has provided a viable strategy for the construction of multiple asymmetric C-C and C-X centres numerous methods have been developed around it synthesis various vital scaffolds. synthetic utility this was enhanced by replacing customary allyl acetates with ethylene diacetates/dicarbonates, vinyl epoxides, oxetanes, carbonates, cyclopropanes, enynes, dienes using transition-metal catalysis. One more milestone achieved when metallaphotocatalysis necessary platform these cascades cheaper metal. This review will provide summary from 2015.

Language: Английский

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