Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Chemical Reviews, Год журнала: 2021, Номер 121(8), С. 4373 - 4505

Опубликована: Март 19, 2021

This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution decarboxylative oxidative substitutions. For each reaction, catalytic data, as well examples of their application to synthesis complex molecules, are collected. Sections which we discuss key aspects for high selectivity a comparison with other metals (with advantages disadvantages) also included. asymmetric substitution, data grouped according type nucleophile employed. Because prominent position use stabilized carbon nucleophiles heteronucleophiles, many chiral ligands have been developed. To better compare results, they presented by ligand types. reactions mainly promoted PHOX or Trost ligands, justifies organizing this section chronological order. results used.

Язык: Английский

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Sequential Visible-Light Photoactivation and Palladium Catalysis Enabling Enantioselective [4+2] Cycloadditions

Journal of the American Chemical Society, Год журнала: 2017, Номер 139(41), С. 14707 - 14713

Опубликована: Сен. 27, 2017

Catalytic asymmetric cycloadditions of reactive ketene intermediates provide new opportunities for the production chiral heterocyclic molecules. Though known over 100 years, ketenes still remain underexplored in field transition-metal (TM)-catalyzed because (1) ketenes, as highly electron-deficient species, are possibly unstable to low-valence TMs (i.e., decarbonylation or aggregation) and (2) conventional thermal synthesis from acyl chlorides amines may be incompatible with TM catalysis chloride amine hydrochloride byproducts). Herein, we detail unprecedented [4+2] cycloaddition vinyl benzoxazinanones a variety via sequential visible-light photoactivation palladium catalysis. It is well demonstrated that traceless transient generation α-diazoketones through visible-light-induced Wolff rearrangement important success present cycloaddition. Furthermore, catalysts new, hybrid P, S ligand enable high reaction selectivity enantiocontrol.

Язык: Английский

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Advances in Palladium‐Catalyzed Decarboxylative Cycloadditions of Cyclic Carbonates, Carbamates and Lactones

ChemCatChem, Год журнала: 2022, Номер 14(9)

Опубликована: Янв. 31, 2022

Abstract Palladium‐catalyzed decarboxylative cycloadditions have emerged as highly effective methods for constructing structurally diverse carbo‐ and heterocycles because of the formation at least two carbon‐carbon or carbon‐heteroatom bonds in a single step. It is great interest to chemists that this type cycloaddition reactions possesses some special advantages such high reactivity, exclusive regioselectivity, good functional group compatibility. Based on these qualities, palladium‐catalyzed present strong ability synthetic chemistry been flourished especially last five years. In review, achievements involving cyclic carbonates, carbamates, lactones accessing oxacyclo‐, azacyclo‐ carbocyclic compounds are addressed. Mechanistic insights applications toward synthesis natural products discussed. The challenges opportunities field also outlined.

Язык: Английский

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Recent Advances in the Catalytic Cycloaddition of 1,n-Dipoles

ACS Catalysis, Год журнала: 2017, Номер 8(1), С. 48 - 58

Опубликована: Ноя. 14, 2017

Dipolar cycloaddition is one of the most valuable methods for synthesizing various carbo- and heterocycles because multiple carbon–carbon carbon–heteroatom bonds form in a single step. Thus, practical generation new 1,n-dipoles control their reactivities are significant aspects modern organic chemistry. Although it quite challenging to handle short-lived 1,n-dipolar species, cycloadditions have been impressively developed recent years. Advancement catalytic abilities has occurred catalyst enables 1,n-dipole enhances selectivities cycloadducts. In this Perspective, achievements synthesize medium-sized heterocyclic compounds addressed. Mechanistic insights applications toward synthesis natural products also discussed.

Язык: Английский

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Transition-metal-catalyzed cyclization reactions using vinyl and ethynyl benzoxazinones as dipole precursors

Tetrahedron Letters, Год журнала: 2018, Номер 59(16), С. 1521 - 1530

Опубликована: Март 6, 2018

Язык: Английский

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Synergetic iridium and amine catalysis enables asymmetric [4+2] cycloadditions of vinyl aminoalcohols with carbonyls

Nature Communications, Год журнала: 2019, Номер 10(1)

Опубликована: Июнь 20, 2019

Abstract Catalytic asymmetric cycloadditions via transition-metal-containing dipolar intermediates are a powerful tool for synthesizing chiral heterocycles. However, within the field of palladium catalysis, compared with well-developed normal electron-demand electrophilic dipolarophiles, general strategy inverse ones nucleophilic dipolarophiles remains elusive, due to inherent linear selectivity in key palladium-catalyzed intermolecular allylations. Herein, based on switched regioselectivity iridium-catalyzed allylations, we achieved two [4+2] vinyl aminoalcohols aldehydes and β,γ-unsaturated ketones through synergetic iridium amine catalysis. The activation by catalysts carbonyls provide foundation subsequent resulting iridium-containing 1,4-dipoles (di)enamine dipolarophiles. former provides straightforward route diverse set enantio-enriched hydroquinolines bearing quaternary stereocenters, later represent an enantio- diastereodivergent synthesis hydroquinolines.

Язык: Английский

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A catalytic asymmetric construction of a tetrahydroquinoline-based spirooxindole framework via a diastereo- and enantioselective decarboxylative [4+2] cycloaddition

Chemical Communications, Год журнала: 2017, Номер 53(72), С. 10030 - 10033

Опубликована: Янв. 1, 2017

A catalytic asymmetric decarboxylative [4+2] cycloaddition of vinyl benzoxazinanones with methyleneindolinones has been established, which provided a series chiral tetrahydroquinoline-based 3,3'-spirooxindoles in high yields (up to 96%) and excellent diastereo- enantioselectivities (all >95 : 5 d.r., up 99% ee). This reaction not only represents the first example enantioselective between Pd-containing 1,4-dipoles, but also demonstrates great practicability cycloadditions synthesis enantio-enriched polycyclic compounds.

Язык: Английский

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Palladium‐Catalyzed Decarboxylative Asymmetric Allylic Alkylation: Development, Mechanistic Understanding and Recent Advances

Advanced Synthesis & Catalysis, Год журнала: 2019, Номер 361(13), С. 3016 - 3049

Опубликована: Фев. 27, 2019

Abstract The palladium‐catalyzed decarboxylative asymmetric allylic alkylation (DAAA) is comprehensively reviewed, from its original development to recent advances in terms of substrate scope, reactivity, regio‐ and enantioselectivity. current understanding the mechanistic details, based on a combination experimental computational studies, described. Selected examples application this synthetic methodology natural product synthesis are given. exploration Pd‐catalyzed catalysis, particular, related interceptive alkylation, has become focus years also summarized. magnified image

Язык: Английский

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Inverse‐Electron‐Demand Palladium‐Catalyzed Asymmetric [4+2] Cycloadditions Enabled by Chiral P,S‐Ligand and Hydrogen Bonding

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(32), С. 11013 - 11017

Опубликована: Май 30, 2019

Catalytic asymmetric cycloadditions of ambident Pd-containing dipolar species with nucleophilic dipolarophiles, namely, inverse-electron-demand cycloadditions, are challenging and underdeveloped. Possibly, the inherent linear selectivity Pd-catalyzed intermolecular allylations lack efficient chiral ligands responsible for this limitation. Herein, two such intermediates deconjugated butenolides azlactones were accomplished by using a novel hybrid P,S-ligand hydrogen bonding. By doing so, highly functionalized, optically active dihydroquinol-2-ones produced generally high reaction efficiencies selectivities. Preliminary DFT calculations performed to explain enantio- diastereoselectivities.

Язык: Английский

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Organocatalytic Intramolecular [4+2] Cycloaddition between In Situ Generated Vinylidene ortho‐Quinone Methides and Benzofurans

Angewandte Chemie International Edition, Год журнала: 2017, Номер 56(44), С. 13722 - 13726

Опубликована: Сен. 4, 2017

Abstract Described herein is the enantioselective construction of oxygen‐containing [5‐6‐5] tricyclic heterocycles by an organocatalyzed asymmetric [4+2] cycloaddition vinylidene ortho ‐quinone methides and benzofurans. According to this methodology, a series with various functional groups were synthesized in excellent enantio‐ diastereoselectivities (>99 % ee , >20:1 d.r.). Furthermore, deuterium‐labeling experiments high‐resolution mass spectroscopy demonstrated that methide intermediate was involved possibly resulted from prototropic rearrangement 2‐ethynylphenol. Remarkably, catalyst loading as low 0.1 mol %, gram‐scale synthesis achieved for transformation.

Язык: Английский

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