Anilines as C‐Nucleophiles in Ir‐Catalyzed Intramolecular Asymmetric Allylic Substitution Reactions

Zhao, Zheng‐Le; Gu, Qianqun; Wu, Xin‐Yan; You, Shu‐Li

doi:10.1002/asia.201701192

Cited by 12 publications

(2 citation statements)

References 121 publications

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“…In the competition between an intermolecular amination and an intramolecular C -alkylation, it was the latter that proceeded faster (Scheme ). The N -substituent R controlled the 268 / 269 ratio of this reaction, which ranged from 4:1 to >19:1 with increasing bulk of R. No reaction occurred with the N -[(benzyloxy)carbonyl]anilines, likely because of insufficient NH acidity. With methyl-protected anilines containing various substituents on the phenyl ring, the products were obtained with high regio- and enantioselectivities.…”

Section: Ir-catalyzed Asymmetric Allylic Alkylationsmentioning

confidence: 99%

Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

et al. 2018

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In this review, we summarize the origin and advancements of iridiumcatalyzed asymmetric allylic substitution reactions during the past two decades. Since the first report in 1997, Ir-catalyzed asymmetric allylic substitution reactions have attracted intense attention due to their exceptionally high regio-and enantioselectivities. Ircatalyzed asymmetric allylic substitution reactions have been significantly developed in recent years in many respects, including ligand development, mechanistic understanding, substrate scope, and application in the synthesis of complex functional molecules. In this review, an explicit outline of ligands, mechanism, scope of nucleophiles, and applications is presented.

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Section: Ir-catalyzed Asymmetric Allylic Alkylationsmentioning

confidence: 99%

Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

et al. 2018

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“…Their fascinating molecular architecture and intriguing biological properties have triggered continuous interest in developing synthetic approaches to build this privileged scaffold for decades . The current catalytic asymmetric methodologies toward chiral THIQs include asymmetric hydrogenation of (dihydro)isoquinolines (Scheme , eq 1), asymmetric nucleophilic addition of cyclic imine intermediates (eq 2), asymmetric Pictet–Spengler reaction and reductive amination of β-phenylethylamine derivatives (eqs 3 and 4), and other miscellaneous reactions . Despite these splendid achievements, most of the existing synthetic protocols can afford only chiral C1-substituted THIQ products, and methods for the direct catalytic enantioselective assembly of polysubstituted THIQs, especially 1,3,4-trisubstituted THIQs, remain rare.…”

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confidence: 99%

Iridium-Catalyzed Asymmetric Cascade Allylation/Pictet–Spengler Cyclization Reaction for the Enantioselective Synthesis of 1,3,4-Trisubstituted Tetrahydroisoquinolines

Yang

Liu

et al. 2021

Org. Lett.

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An iridium-catalyzed trifluoroacetic acid-promoted asymmetric cascade allylation/Pictet–Spengler cyclization reaction of azomethine ylides with aromatic allylic alcohols is reported. This protocol provides a facile and scalable method for the construction of 1,3,4-trisubstituted tetrahydroisoquinolines containing two stereogenic centers in good yields (up to 96%) with generally excellent diastereo- and enantioselectivities (up to >20:1 dr and >99% ee). Furthermore, a series of aromatic heterocycle-fused piperidines were also obtained with excellent enantiocontrol by this methodology.

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Iridium‐Catalyzed, Enantioselective, Allylic Alkylations With Carbon Nucleophiles

Helmchen

Yang

et al. 2019

Organic Reactions

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Iridium‐catalyzed, enantioselective allylic alkylation is a powerful method for the construction of a stereogenic center adjacent to a vinyl group. The starting materials are readily available, generally either branched allylic alcohols or esters of linear allylic alcohols. The reaction is compatible with a wide variety of functional groups and generally proceeds with very high enantio‐ and site selectivity. Mechanistic aspects, as well as reaction methods, are presented in detail. The scope of the method is defined primarily by the nucleophilic component. Compounds that are CH‐acidic, such as malonic acid derivatives, β‐keto esters, iminoglycinates, azlactones, aliphatic nitro compounds, and sulfones are employed, often without stoichiometric amounts of base. Diastereomers are formed in the case of prochiral nucleophiles; the control of diastereoselectivity by dual catalysis, using both an iridium and an organocatalyst, is very efficient. Other nucleophilic components include silyl enol ethers, enamines, alkenes, and arenes, in particular, heterocycles. The application of the latter in cyclization reactions, such as polyene cyclizations and dearomatizations, furnishes highly complex structures with excellent stereocontrol. Finally, applications in natural product synthesis and medicinal chemistry are presented, as well as experimental procedures.

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Anilines as C‐Nucleophiles in Ir‐Catalyzed Intramolecular Asymmetric Allylic Substitution Reactions

Cited by 12 publications

References 121 publications

Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

Iridium-Catalyzed Asymmetric Cascade Allylation/Pictet–Spengler Cyclization Reaction for the Enantioselective Synthesis of 1,3,4-Trisubstituted Tetrahydroisoquinolines

Iridium‐Catalyzed, Enantioselective, Allylic Alkylations With Carbon Nucleophiles

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