High-order dipolar annulations with metal-containing reactive dipoles

Chemical Society Reviews, Год журнала: 2022, Номер 51(10), С. 4146 - 4174

Опубликована: Янв. 1, 2022

The advances on metal-catalysed high-order dipolar annulations were comprehensively summarized in this review. To further exploit the potential of unique annulation strategy, a research outlook was also proposed.

Язык: Английский

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Asymmetric (4 + 3) and (4 + 1) Annulations of Isatin-derived Morita–Baylis–Hillman Carbonates to Construct Diverse Chiral Heterocyclic Frameworks

Organic Letters, Год журнала: 2020, Номер 22(11), С. 4240 - 4244

Опубликована: Май 15, 2020

A chiral tertiary amine-catalyzed asymmetric γ-regioselective (4 + 3) annulation reaction of isatin-derived Morita-Baylis-Hillman carbonates and 1-azadienes was developed, delivering azepane spirooxindoles with excellent stereoselectivity. In addition, by tuning the substituents carbonates, switchable γ-(4 or α-(4 1) o-quinone methides observed to furnish benzo[b]oxepines 2,3-dihydrobenzofurans, respectively, under similar catalytic conditions.

Язык: Английский

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Regiodivergent Synthesis of Spirocyclic Compounds through Pd‐Catalyzed Regio‐ and Enantioselective [3+2] Spiroannulation

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(11), С. 5806 - 5810

Опубликована: Янв. 21, 2021

Abstract A novel Pd 0 ‐catalyzed highly regio‐ and enantioselective [3+2] spiroannulation reaction has been developed for rapid assembly of a new class [5,5] spirocyclic carbo‐ heterocycles. Notably, the regioselectivity could be dominated by fine‐tuning Pd‐π‐allyl intermediate. An array coupling partners well‐tolerated with excellent regio‐, enantioselectivities. Moreover, potential application this was exemplified several further transformations.

Язык: Английский

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Transition‐Metal‐Catalyzed Cycloaddition Reactions to Access Seven‐Membered Rings

Chemistry - A European Journal, Год журнала: 2020, Номер 26(67), С. 15354 - 15377

Опубликована: Июль 24, 2020

Abstract The efficient and selective synthesis of functionalized seven‐membered rings remains an important pursuit within synthetic organic chemistry, as this motif appears in numerous drug‐like molecules natural products. Use cycloaddition reactions attractive approach for their construction the perspective atom step economy. Additionally, ability to combine multiple components a single reaction has potential allow combinatorial strategies diversity‐oriented synthesis. inherent entropic penalty associated with achieving these transformations impressively been overcome development catalysis, whereby can be pre‐organized through activation by transition‐metal‐catalysis. fine‐tuning metal/ligand combinations well conditions allows chemo‐, regio‐, diastereo‐ enantioselectivity transformations. Herein, we discuss recent advances transition‐metal‐catalyzed via combination 2–4 mediated variety metals. An emphasis is placed on mechanistic aspects both illustrate state science highlight unique application novel processes transition‐metals

Язык: Английский

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Access to 5,6-Spirocycles Bearing Three Contiguous Stereocenters via Pd-Catalyzed Stereoselective [4 + 2] Cycloaddition of Azadienes

Organic Letters, Год журнала: 2021, Номер 23(8), С. 2884 - 2889

Опубликована: Март 26, 2021

We present herein a highly diastereo- and enantioselective Pd-catalyzed [4 + 2] cycloaddition of benzofuran-derived azadienes with vinyl benzoxazinanones, which represents rare stereoselective this class fused as two-atom synthon. The use phosphoramidite ligand bearing chiral secondary amine simple biphenyl backbone proved to be the key construct novel spirocyclic tetrahydroquinoline scaffold containing three contiguous stereocenters single diastereomer in high enantioselectivity.

Язык: Английский

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Ligand-Controlled, Palladium-Catalyzed Asymmetric [4+4] and [2+4] Cycloadditions

Organic Letters, Год журнала: 2021, Номер 23(6), С. 2292 - 2297

Опубликована: Март 8, 2021

Ligand-controlled, palladium-catalyzed asymmetric [4+4] and [2+4] cycloaddition reactions of benzofuran-derived azadienes have been developed. Taking advantage chiral P,N-ligand (S,Rp)-PPFA, we obtained a variety benzofuro[2,3-c][1,5] oxazocines in good yields with excellent enantioselectivities via reactions. Employing P,P-ligand (S)-Cl-MeO-BIPHEP, the chemo- regioselectivities were switched to synthesize tetrahydropyran-fused spirocyclic compounds efficiency

Язык: Английский

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Recent advances in Pd-catalyzed asymmetric cyclization reactions

Chemical Society Reviews, Год журнала: 2023, Номер 53(2), С. 883 - 971

Опубликована: Дек. 18, 2023

This review aims to collect advancements in enantioselective palladium-catalyzed cyclization reactions over the past eleven years, and it is organized into thirteen sections depending on different types of transformations involved.

Язык: Английский

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Palladium-Catalyzed Enantioselective Cycloadditions of Aliphatic 1,4-Dipoles: Access to Chiral Cyclohexanes and Spiro [2.4] heptanes

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(43), С. 18628 - 18636

Опубликована: Окт. 14, 2020

Design and exploration of new intermediates for chemo-, regio-, stereoselective cycloadditions remain a formidable challenge in modern organic synthesis. Compared to the well-developed 1,3-dipolar cycloadditions, Pd-catalyzed1,4-dipolar are generally limited specialized substrates due inherent nature thermodynamically driven intramolecular transformations undesired isomerizations. Herein, we demonstrate use ligated palladium catalysts control modulate intermolecular reactivity aliphatic 1,4-dipoles, enabling two distinctive cycloaddition pathways with broad scope acceptors. This atom-economic process also features an eco-friendly situ deprotonation strategy generate corresponding active palladium-mediated dipoles. Overall, diverse array chiral 6-membered rings spiro [2.4] heptanes were prepared high yield selectivity. In addition, unexpected property cyano-stabilized carbanions was discovered investigated, which can be useful designing predicting future transformations.

Язык: Английский

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Direct access to spirocycles by Pd/WingPhos-catalyzed enantioselective cycloaddition of 1,3-enynes

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Сен. 27, 2021

Abstract Spirocycles play an important role in drug discovery and development. The direct, catalytic, enantioselective synthesis of spirocycles from readily available starting materials atom economic manner remains a highly sought-after task organic synthesis. Herein, Pd-hydride-catalyzed cycloaddition method for the spirocyclic compounds directly two classes commonly materials, 1,3-enynes cyclic carbon−hydrogen (C−H) bonds, is reported. reactions employ chiral Pd/WingPhos catalyst to both suppress formation bis-allenyl by-products control stereoselectivity. 1,3-Enynes are used as dielectrophilic four-carbon units reactions, which also enables enyne substrate-directed enantioselectivity switch with good levels stereocontrol. present spirocycle tolerates broad range functional groups 1,3-enyne substrates, including alcohols, esters, nitriles, halides, olefins. A variety diverse nucleophiles, pharmaceutically heterocycles carbocycles, can be flexibly incorporated spiro scaffolds.

Язык: Английский

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Palladium-Catalyzed Enantioselective Cycloaddition of Carbonylogous 1,4-Dipoles: Efficient Access to Chiral Cyclohexanones

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(52), С. 21645 - 21650

Опубликована: Дек. 18, 2020

A novel palladium-mediated carbonylogous 1,4-dipole was developed by in situ deprotonation. By using our own-developed C2-unsymmetric phosphoramidite as supporting ligand, this dipole applied to the asymmetric synthesis of chiral cyclohexanones via a catalytic [4+2] cycloaddition. Electron-deficient allylic carbonate used generate highly reactive dipoles for first time, and diverse array stable precursors explored elaboration cyclohexanones. general mechanism reaction process stereochemical outcome proposed, which can be useful designing predicting future transformation.

Язык: Английский

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