Controlling Stereoselectivity with Noncovalent Interactions in Chiral Phosphoric Acid Organocatalysis

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Chiral phosphoric acids (CPAs) have emerged as highly effective Brønsted acid catalysts in an expanding range of asymmetric transformations, often through novel multifunctional substrate activation modes. Versatile and broadly appealing, these benefit from modular tunable structures, compatibility with additives. Given the unique types noncovalent interactions (NCIs) that can be established between CPAs various reactants─such hydrogen bonding, aromatic interactions, van der Waals forces─it is unsurprising catalyst systems become a promising approach for accessing diverse chiral product outcomes. This review aims to provide in-depth exploration mechanisms by which impart stereoselectivity, positioning NCIs central feature connects broad spectrum catalytic reactions. Spanning literature 2004 2024, it covers nucleophilic additions, radical atroposelective bond formations, highlighting applicability CPA organocatalysis. Special emphasis placed on structural mechanistic features govern CPA-substrate well tools techniques developed enhance our understanding their behavior. In addition emphasizing details stereocontrolling elements individual reactions, we carefully structured this natural progression specifics broader, class-level perspective. Overall, findings underscore critical role catalysis significant contributions advancing synthesis.

Language: Английский

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Asymmetric dearomative single-atom skeletal editing of indoles and pyrroles

Nature Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

Language: Английский

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Catalytic Enantioselective Aminative Difunctionalization of Alkenes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(10), P. 7029 - 7038

Published: March 1, 2024

Enantioselective difunctionalization of alkenes offers a straightforward means for the rapid construction enantioenriched complex molecules. Despite tremendous efforts devoted to this field, enantioselective aminative remains challenge, particularly through an electrophilic addition fashion. Herein, we report unprecedented approach via copper-catalyzed with external azo compounds as nitrogen sources. A series valuable cyclic hydrazine derivatives either [3 + 2] cycloaddition or intramolecular cyclization have been achieved in high chemo-, regio-, enantio-, and diastereoselectivities. In transformation, wide range functional groups, such carboxylic acid, hydroxy, amide, sulfonamide, aryl could serve nucleophiles. Importantly, new cyano oxazoline chiral ligand was found play crucial role control enantioselectivity.

Language: Английский

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Photoinduced Pd-Catalyzed Dearomative 2,5-Difunctionalizition of Furans via Cascade C–C/C–O Bond Formation

Organic Letters, Journal Year: 2024, Volume and Issue: 26(5), P. 1083 - 1087

Published: Jan. 26, 2024

We report an efficient and mild approach for radical dearomatization via photoinduced palladium-catalyzed reaction of three components (i.e., furans, alcohols, bromoalkanes). In this strategy, various functionalized spiro-heterocycles were prepared from furans in one step cascade C–C/C–O bond formation under redox neutral conditions.

Language: Английский

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Halogencarbene-free Ciamician-Dennstedt single-atom skeletal editing

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 19, 2024

Single-atom skeletal editing is an increasingly powerful tool for scaffold hopping-based drug discovery. However, the insertion of a functionalized carbon atom into heteroarenes remains rare, especially when performed in complex chemical settings. Despite more than century research, Ciamician-Dennstedt (C-D) rearrangement limited to halocarbene precursors. Herein, we report general methodology reaction using α-halogen-free carbenes generated situ from N-triftosylhydrazones. This one-pot, two-step protocol enables various carbenes, including those previously unexplored C-D chemistry, indoles/pyrroles scaffolds access 3-functionalized quinolines/pyridines. Mechanistic studies reveal pathway involving intermediacy 1,4-dihydroquinoline intermediate, which could undergo oxidative aromatization or defluorinative form different carbon-atom products. Ciamician–Dennstedt authors

Language: Английский

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Cobalt‐Catalyzed Wagner–Meerwein Rearrangements with Concomitant Nucleophilic Hydrofluorination

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(35)

Published: July 6, 2023

We report a cobalt-catalyzed Wagner-Meerwein rearrangement of gem-disubstituted allylarenes that generates fluoroalkane products with isolated yields up to 84 %. Modification the counteranion N-fluoropyridinium oxidant suggests substrates undergo nucleophilic fluorination during reaction. Subjecting other known metal-mediated hydrofluorination procedures did not lead observable 1,2-aryl migration. Thus, indicating unique ability these conditions generate sufficiently reactive electrophilic intermediate capable promoting this rearrangement.

Language: Английский

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Fully atom-economic access to spiro-cyclic skeletons through photoredox-induced hydrogen transfer/Giese addition/dearomative cyclization/protonation cascade

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(11), P. 3165 - 3172

Published: Jan. 1, 2024

Amine-tethered spiro-cyclic skeletons were obtained through photo-induced 100%-atom-economic dearomatization, involving the cleavage of α-C(sp 3 )–H amines. Pentacyclic framework was achieved from pyridinyl ring within two steps.

Language: Английский

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Enantioselective Synthesis of Bicyclo[3.2.1]octadienes via Palladium‐Catalyzed Intramolecular Alkene‐Alkyne Coupling Reaction

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(51)

Published: Nov. 3, 2023

Bicyclo[3.2.1]octadiene compounds and derivatives exist in a number of natural products bioactive compounds. Nevertheless, catalytic enantioselective protocols for the synthesis these skeletons have not been disclosed. Herein we reported palladium-catalyzed asymmetric intramolecular alkene-alkyne coupling alkyne-tethered cyclopentenes, affording library enantionenriched bicyclo[3.2.1]octadienes excellent yields enantioselectivities (mostly >99 % ee). Moreover, could undergo an unusual iodination-induced 1,2-acyl migration, forming iodinated with three vicinal stereocenters. The enone isolated olefin motifs embedded provide useful handles downstream elaboration.

Language: Английский

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Chiral phosphoric acid (CPA)-catalyzed transformation reaction of ketene: Competing mechanisms and origin of regio- and stereoselectivities

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 560, P. 114150 - 114150

Published: April 16, 2024

Language: Английский

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Switchable Skeletal Rearrangement of Hexahydro-4H-indol-4-ones: Divergent Synthesis of Dihydroxy-4H-cyclopenta[b]pyridin-4-ones and 8-Alkenyl Oxepane-2,6-diones

Organic Letters, Journal Year: 2024, Volume and Issue: 26(20), P. 4205 - 4211

Published: May 14, 2024

An unprecedented base-controlled selective skeletal rearrangement reaction of hexahydro-4

Language: Английский

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