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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Acyclic Quaternary Carbon Stereocenters via Enantioselective Transition Metal Catalysis

Chemical Reviews, Год журнала: 2017, Номер 117(19), С. 12564 - 12580

Опубликована: Сен. 14, 2017

Whereas numerous asymmetric methods for formation of quaternary carbon stereocenters in cyclic systems have been documented, the construction acyclic with control absolute stereochemistry remains a formidable challenge. This Review summarizes enantioselective from achiral or chiral racemic reactants via transition metal catalysis.

Язык: Английский

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Asymmetric, visible light-mediated radical sulfinyl-Smiles rearrangement to access all-carbon quaternary stereocentres

Nature Chemistry, Год журнала: 2021, Номер 13(4), С. 327 - 334

Опубликована: Апрель 1, 2021

Язык: Английский

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Palladium-Catalyzed Asymmetric Allylic Alkylation Strategies for the Synthesis of Acyclic Tetrasubstituted Stereocenters

Synthesis, Год журнала: 2018, Номер 51(01), С. 1 - 30

Опубликована: Дек. 5, 2018

Over the past 20 years, asymmetric synthesis of acyclic tetrasubstituted stereocenters by Pd-catalyzed allylic alkylation (Pd-AAA) strategies has seen considerable growth. Despite inherent difficulty in accessing stereocenters, creative approaches toward this problem have resulted high stereoinduction on both electrophilic and nucleophilic reaction partners. Much chemistry paved way for unique solutions Mo-, Ir-, Rh-AAA, with many complimentary methods arising due to regiochemical outcomes AAA outside Pd catalysis. 1 Introduction 2 Stereocontrol Prochiral Electrophiles 3 Nucleophiles 4 Temporary Cyclic Pronucleophiles 5 Allylic Alkylation Other Metals 6 Conclusions Outlook

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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Catalytic Enantioselective Alkylation of Prochiral Enolates

Chemical Reviews, Год журнала: 2021, Номер 121(15), С. 9196 - 9242

Опубликована: Июль 26, 2021

The asymmetric alkylation of enolates is a particularly versatile method for the construction α-stereogenic carbonyl motifs, which are ubiquitous in synthetic chemistry. Over past several decades, focus has shifted to development new catalytic methods that depart from classical stoichiometric stereoinduction strategies (e.g., chiral auxiliaries, alkali metal amide bases, electrophiles, etc.). In this way, enantioselective prochiral greatly improves step- and redox-economy process, addition enhancing scope selectivity these reactions. review, we summarize origin advancement enolate methods, with directed emphasis on union nucleophiles carbon-centered electrophiles derivatives. Hence, transformative developments each distinct class nucleophile ketone enolates, ester etc.) presented modular format highlight state-of-the-art current limitations area.

Язык: Английский

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Catalytic Enantioselective Primary C–H Borylation for Acyclic All-Carbon Quaternary Stereocenters

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(2), С. 1635 - 1643

Опубликована: Янв. 5, 2024

Creating a perfect catalyst to operate enzyme-like chiral recognition has been long-sought aim. A challenging example in this context is constructing acyclic all-carbon quaternary stereogenic centers by transition metal-catalyzed enantioselective C–H activation. We now report highly iridium-catalyzed primary borylation of α-all-carbon substituted 2,2-dimethyl amides enabled tailor-made bidentate boryl ligand (CBL). The success the current transformation attributed CBL/iridium catalyst, which confined pocket. This protocol provides diverse array stereocenters with excellent enantiocontrol and distinct structural features. Computational study reveals that steric hindrance CBL could regulate type dominant orbital interaction between substrate, crucial conferring high induction.

Язык: Английский

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Stereodivergent conjugate reduction of α-substituted α,β-unsaturated N-sulfinyl ketimines: flexible access to challenging acyclic β,β-disubstituted enesulfinamides

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(4), С. 1218 - 1224

Опубликована: Янв. 1, 2024

Stereodivergent 1,4-reduction to provide flexible access the challenging acyclic enesulfinamides featuring two electronically and sterically similar β-substituents.

Язык: Английский

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Enantioselective Construction of Quaternary Stereocenters via A Chiral Spiro Phosphoric Acid-Assisted Formal Gold Carbene gem-Dialkylation Reaction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 19261 - 19270

Опубликована: Июль 1, 2024

Enantioselective construction of all-carbon quaternary stereocenters has attracted much attention over the past few decades. A variety catalytic asymmetric methods have been disclosed based on use presynthesized complex reagents that impart congested steric hindrance to reaction center, which generally produce chiral molecules through forming one C-C bond. The readily available could build two bonds same carbonic center with concomitant assembly remains challenging. Herein, we disclose a alkyne multifunctionalization using gold and spiro phosphoric acid (SPA) for synergistic catalysis. In this method, accessible internal alkynes served as key carbene precursors, followed by

Язык: Английский

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α-Quaternary Chiral Aldehydes from Styrenes, Allylic Alcohols, and Syngas via Multi-catalyst Relay Catalysis

Chem, Год журнала: 2018, Номер 4(5), С. 1047 - 1058

Опубликована: Апрель 5, 2018

Язык: Английский

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