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

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(8), P. 4373 - 4505

Published: March 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.

Language: Английский

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Synthesis and applications of sodium sulfinates (RSO₂Na): a powerful building block for the synthesis of organosulfur compounds

RSC Advances, Journal Year: 2021, Volume and Issue: 11(16), P. 9130 - 9221

Published: Jan. 1, 2021

This review provides a unique and comprehensive overview of sodium sulfinates for synthesizing many valuable sulfur-containing compounds, such as thiosulfonates, sulfonamides, sulfides, sulfones, allyl vinyl sulfones β-keto sulfones.

Language: Английский

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Photoinduced, Palladium-Catalyzed Enantioselective 1,2-Alkylsulfonylation of 1,3-Dienes

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3725 - 3732

Published: Feb. 21, 2024

The chiral allylic sulfonylated group is a unique structural motif embedded in range of natural products and pharmaceuticals. Notably, the synthesis structurally diverse derivatives via alkylsulfonylation 1,3-dienes remains underexplored because its inherent challenges stereocontrol regioselectivity. Herein, photoinduced, palladium-catalyzed enantioselective 1,2-alkylsulfonylation conjugated described. A wide variety alkyl bromides, 1,3-dienes, sodium sulfinates could be facilely coupled to generate value-added with high enantioselectivity. Finally, utility this difunctionalization protocol was demonstrated pharmaceutical analogue synthesis.

Language: Английский

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Palladium-Catalyzed Regio- and Enantioselective Hydrosulfonylation of 1,3-Dienes with Sulfinic Acids: Scope, Mechanism, and Origin of Selectivity

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(37), P. 15860 - 15869

Published: Aug. 19, 2020

Chiral sulfones are important structural motifs in organic synthesis because of their widespread use pharmaceutical chemistry. In particular, chiral allylic have drawn particular interest synthetic utility. However, enantioselective 1,3-disubstituted unsymmetrical remains a challenge. this article, we report protocol for (R)-DTBM-Segphos/Pd-catalyzed regio- and hydrosulfonylation 1,3-dienes with sulfinic acids, which provides atom- step-economical access to sulfones. The reaction occurs under mild conditions has broad substrate scope. Combined experimental computational studies suggest that the is initiated by ligand-to-ligand hydrogen transfer followed C–S bond reductive elimination via six-membered transition state. Steric repulsion between olefinic C–H tert-butyl group (R)-DTBM-Segphos was found be key factor enantiocontrol.

Language: Английский

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An Update of Transition Metal-Catalyzed Decarboxylative Transformations of Cyclic Carbonates and Carbamates

Molecules, Journal Year: 2019, Volume and Issue: 24(21), P. 3930 - 3930

Published: Oct. 31, 2019

Functionalized cyclic organic carbonates and carbamates are frequently used in a number of transition metal-catalyzed decarboxylative reactions for the construction interesting molecules. These transformations have attracted more research attention recent years mainly due to their advantages less waste generation versatile reactivities. On basis previous reviews on this hot topic, present review will focus development functionalized last two years.

Language: Английский

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Palladium‐Catalyzed Asymmetric Hydrosulfonylation of 1,3‐Dienes with Sulfonyl Hydrazides

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(6), P. 2948 - 2951

Published: Oct. 23, 2020

A highly enantio- and regioselective hydrosulfonylation of 1,3-dienes with sulfonyl hydrazides has been realized by using a palladium catalyst containing monodentate chiral spiro phosphoramidite ligand. The reaction provided an efficient approach to synthetically useful allylic sulfones. Mechanistic studies suggest that the proceeds through formation allyl hydrazine intermediate subsequent rearrangement sulfone product. transformation product is enantioselectivity-determining step.

Language: Английский

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Enantioselective Hydrothiolation: Diverging Cyclopropenes through Ligand Control

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(16), P. 6176 - 6184

Published: April 15, 2021

In this article, we advance Rh-catalyzed hydrothiolation through the divergent reactivity of cyclopropenes. Cyclopropenes undergo to provide cyclopropyl sulfides or allylic sulfides. The choice bisphosphine ligand dictates whether pathway involves ring-retention ring-opening. Mechanistic studies reveal origin for switchable selectivity. Our results suggest two pathways share a common cyclopropyl-Rh(III) intermediate. Electron-rich Josiphos ligands promote direct reductive elimination from intermediate afford in high enantio- and diastereoselectivities. Alternatively, atropisomeric (such as DTBM-BINAP) enable ring-opening generate with regiocontrol.

Language: Английский

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Copper‐Catalyzed Remote Enantioselective Sulfonylation of Yne‐Allylic Esters with Sodium Sulfinates

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(52)

Published: Nov. 13, 2023

Impressive progress has been made in the copper-catalyzed asymmetric propargylic substitution (APS) reaction, but its use remote yne-allylic remains a challenging topic. Herein, we report first enantioselective sulfonylation of esters with sodium sulfinates. The reaction is assumed to occur via copper-vinylvinylidene species as key reactive intermediate. readily available starting materials, mild conditions, and excellent regio-, enantio- stereoselectivity, well broad substrate scope (>70 examples), show practicality attractiveness this method.

Language: Английский

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A general copper-catalysed enantioconvergent C(sp3)–S cross-coupling via biomimetic radical homolytic substitution

Nature Chemistry, Journal Year: 2023, Volume and Issue: 16(3), P. 466 - 475

Published: Dec. 6, 2023

Language: Английский

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Asymmetric Synthesis of 2,2‐Difluorotetrahydrofurans through Palladium‐Catalyzed Formal [3+2] Cycloaddition

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(44), P. 23641 - 23645

Published: Sept. 8, 2021

The asymmetric synthesis of 2,2-difluorinated tetrahydrofurans was accomplished via enantioselective formal [3+2] cycloaddition catalyzed by palladium. reaction between gem-difluoroalkenes and racemic vinyl epoxides or vinylethylene carbonates resulted in the formation enantioenriched 2,2-difluorotetrahydrofurans with an enantioselectivity up to 98 %. Notably, used readily available (R)-BINAP as ligand at a low loading yielded wide variety difluorinated products moderate high yields. Both chiral diastereomers could be obtained single sequence.

Language: Английский

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