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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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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Further Developments and Applications of Oxazoline-Containing Ligands in Asymmetric Catalysis

Chemical Reviews, Год журнала: 2021, Номер 121(11), С. 6373 - 6521

Опубликована: Май 21, 2021

The chiral oxazoline motif is present in many ligands that have been extensively applied a series of important metal-catalyzed enantioselective reactions. This Review aims to provide comprehensive overview the most significant applications oxazoline-containing reported literature starting from 2009 until end 2018. are classified not by reaction which their metal complexes but nature denticity, chirality, and donor atoms involved. As result, continued development ligand architectural design mono(oxazolines), bis(oxazolines), tris(oxazolines) tetra(oxazolines) variations thereof can be more easily monitored reader. In addition, key transition states selected asymmetric transformations will given illustrate features give rise high levels induction. further aid reader, we summarize majority schemes with representative examples highlight variation % yields ees for carefully substrates. should particular interest experts field also serve as useful point new researchers this area. It hoped stimulate both development/design novel transformations.

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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Ternary Catalysis Enabled Three-Component Asymmetric Allylic Alkylation as a Concise Track to Chiral α,α-Disubstituted Ketones

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(49), С. 20818 - 20827

Опубликована: Дек. 6, 2021

Multicomponent reactions that involve interception of onium ylides through Aldol, Mannich, and Michael addition with corresponding bench-stable acceptors have demonstrated broad applications in synthetic chemistry. However, because the high reactivity transient survival these situ generated intermediates, substitution-type process, especially asymmetric catalytic version, remains hitherto unknown. Herein, a three-component allylation α-diazo carbonyl compounds alcohols allyl carbonates is disclosed by employing ternary cooperative catalysis achiral Pd-complex, Rh2(OAc)4, chiral phosphoric acid CPA. This method represents first example allylic alkylation an SN1-type trapping which involves convergent assembly two active Pd-allyl species, enol derived from ylides, providing expeditious access to α,α-disubstituted ketones good yields excellent enantioselectivity. Combined experimental computational studies shed light on mechanism this novel reaction, including critical role Xantphos ligand origin

Язык: Английский

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Evolution in heterodonor P-N, P-S and P-O chiral ligands for preparing efficient catalysts for asymmetric catalysis. From design to applications

Coordination Chemistry Reviews, Год журнала: 2021, Номер 446, С. 214120 - 214120

Опубликована: Июль 19, 2021

The success of phosphine-oxazoline ligands (PHOX) inspired the progress in P-oxazoline ligand families by modifying either backbone, electronic and/or steric properties phosphine group or exchanging to a phosphinite phosphite group. In this respect, structures chiral have become more diverse and new very efficient emerged, which improved catalytic performance some asymmetric transformations, with an increased versatility, both range reactions substrates/reagents. addition, most are synthesized from easily accessible amino alcohols, maintaining short synthetic route developed for PHOX ligands. New been replacing oxazoline functionality several other N-donor groups, e.g. imidazole, thiazole, oxazole, pyridine, etc., O- S-groups. This review offers critical overview utility these successful bidentate heterodonor P-N, P-O P-S applied metal-mediated processes. We illustrate how, through proper design, can be excellent source ligands, superior many than best C2-symmetric N,N P,P-ligands reported so far.

Язык: Английский

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Tandem Dearomatization/Enantioselective Allylic Alkylation of Pyridines

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(22), С. 11907 - 11913

Опубликована: Май 22, 2023

Herein, we report a multistep one-pot reaction of substituted pyridines leading to N-protected tetrahydropyridines with outstanding enantioselectivity (up 97% ee). An iridium(I)-catalyzed dearomative 1,2-hydrosilylation enables the use N-silyl enamines as new type nucleophile in subsequent palladium-catalyzed asymmetric allylic alkylation. This telescoped process overcomes intrinsic nucleophilic selectivity synthesize enantioenriched, C-3-substituted tetrahydropyridine products that have been otherwise challenging access.

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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