Synthesis of chiral sulfones via nickel-catalyzed asymmetric hydrogenation

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(10), P. 2786 - 2792

Published: Jan. 1, 2024

A Ni-catalyzed highly enantioselective hydrogenation of α,β-unsaturated sulfones was successfully realized achieving high yields (91–98%) and excellent enantioselectivities (up to 99.9% ee).

Language: Английский

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Earth‐Abundant Nickel‐Catalyzed Asymmetric Hydrogenation^†

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(23), P. 3135 - 3156

Published: Aug. 13, 2024

Comprehensive Summary Transition metal‐catalyzed asymmetric hydrogenation is an efficient and direct synthetic method to access chiral compounds, which features simplicity, easy working‐up process, high atomic economy. It typically relies on precious transition metal catalytic systems, including ruthenium, rhodium, iridium palladium, always face the difficulties of limited resources, cost, environmental contamination. Therefore, great efforts were made apply earth‐abundant, low (non‐)toxic, environmentally friendly metals, such as iron, cobalt, nickel copper, in past decades, some considerable breakthroughs have been obtained. In this review, we mainly summarized recent research progress nickel‐catalyzed prochiral unsaturated molecules, olefins, imines ketones. And continuous development systems application them into challenging prospected future. Key Scientists has regarded important approach molecules. The first example homogeneous was developed by Knowles Horner 1968, respectively. 1971, Kagan privileged DIOP ligand for hydrogenation. Halpern Brown deep studies Rh‐catalyzed 1977, Noyori a powerful BINAP 1980. Owing Noyori's contribution field hydrogenation, they awarded Nobel Prize Chemistry 2001. 1984, Ohkubo pioneering earth‐abundant Ni‐catalyzed ethyl α‐methylcrotonate. A many scientists tremendous ligands, as, Bosnich, Kumada, Giongo, Takaya, Miyashima, Achiwa, Burk, Pflaltz, Chan, X. Zhang, Imamoto, Zhou, Genet, Sannicolo, Ding, Hoge, W. Z. Tang, these ligands owned wide addition, Fan investigation aromatic heterocyclic compounds. importance (transfer) promoted cheap researchers, Hamada, Gao, J. S. Chirik, Y.‐G. Lv, Dong, Fu, Deng, Hou, there are other that also transformation, with too space list all them.

Language: Английский

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Highly enantioselective Ni-catalyzed asymmetric hydrogenation of β,β-disubstituted acrylic acids

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(16), P. 4472 - 4477

Published: Jan. 1, 2022

A highly enantioselective Ni-catalyzed hydrogenation of β,β-disubstituted acrylic acids was first realized using Ph-BPE, providing straightforward access to chiral carboxylic in high yields with excellent enantioselectivities, up 99% ee.

Language: Английский

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Iron/photoredox dual catalysis for acyl nitrene-based C–O bond formation towards phthalides

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(98), P. 13644 - 13647

Published: Jan. 1, 2022

This paper describes iron/photoredox dual-catalyzed acyl nitrene formation and the use of in constructing various C-O bonds towards phthalides. The developed reaction starts from N-methoxyl-2-alkylbenzamides. Mechanism surveys suggest involves iron nitrene-based hydrogen atom abstraction (HAA), radical-polar crossover O-nucleophilic SN1. Distinctively, often-reported radical rebound previous publications is not observed. represents first example on synthesis Moreover, it also serves as a supplement for marketed medicines such 3-butylphthalides (NBP), thalidomide, Pomalyst Otezia.

Language: Английский

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Photocatalytic Three-Component Acylcarboxylation of Alkenes with CO₂

Organic Letters, Journal Year: 2024, Volume and Issue: 26(30), P. 6491 - 6496

Published: July 18, 2024

γ-Keto acid is a valuable chemical motif in wide range of fields including organic, biological, and medicinal chemistry. However, its single-step synthesis challenging because the mismatch carbonyl polarity low tolerance carboxylic acids. Herein, we report syntheses γ-keto acids using alkenes CO

Language: Английский

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Access to Alkenyl Cyclobutanols by Ni‐Catalyzed Regio‐ and Enantio‐selective syn‐Hydrometalative 4‐exo‐trig Cyclization of Alkynones

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 12, 2024

Abstract Enantioselective synthesis of (spiro)cyclobutane derivatives poses significant challenges yet holds promising applications for both synthetic and medicinal chemistry. We report here a nickel‐catalyzed asymmetric syn ‐hydrometalative 4‐ exo ‐ trig cyclization 1,4‐alkynones to synthesize alkenyl cyclobutanols with tetrasubstituted stereocenter. This strategy features broad substrate scope, delivering variety trifluoromethyl‐containing rigid (spiro)carbocycle skeletons in good yields high enantioselectivities (up 84 % yield 98.5 : 1.5 er). The utility is demonstrated through stereospecific transformations into fused spiro molecules. Experimental computational mechanistic studies indicate that the reaction initiated by an active Ni−H species, carbonyl‐directed hydrometalation as key regioselective control. catalytic method provides general solution hydrofunctionalization alkynes represents efficient pattern assembling highly strained enantioenriched bioisosteres.

Language: Английский

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Visible-Light-Promoted Carbene Insertion and Decarbonylation for the Synthesis of α-Substituted γ-Ketoesters

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(19), P. 13352 - 13362

Published: Sept. 21, 2022

Herein, we report a blue visible-light-promoted approach for preparing variety of α-substituted γ-ketoester derivatives through carbene insertion and the decarbonylation enaminones diazoesters. These reactions use readily available starting materials transition-metal-free, eco-friendly procedures that are amenable to gram-scale synthesis wide functional group tolerance. This methodology may be useful constructing polysubstituted heterocycles with potential biological activity.

Language: Английский

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The Proton of Alcohols as Hydrogen Source in Diboron-Mediated Nickel-Catalyzed Asymmetric Transfer Hydrogenation of Cyclic N-Sulfonyl Imines

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 89(1), P. 710 - 718

Published: Dec. 15, 2023

The proton of alcohols as the sole hydrogen source in diboron-mediated nickel-catalyzed asymmetric transfer hydrogenation cyclic N-sulfonyl imines has been developed, providing chiral sulfamidates excellent enantioselectivities. mechanistic investigations suggested that could be activated by tetrahydroxydiboron to form active nickel hydride species.

Language: Английский

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RuPHOX-Ru catalyzed asymmetric Guerbet reaction of secondary alcohols with primary alcohols

Tetrahedron, Journal Year: 2023, Volume and Issue: 143, P. 133543 - 133543

Published: July 11, 2023

Language: Английский

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Divergent Synthesis of β‐Hydroxy Amides (Esters) and γ‐Amino Alcohols via Ir/f‐Diaphos Catalyzed Asymmetric Hydrogenation

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(17), P. 3074 - 3080

Published: July 12, 2022

Abstract The iridium/ f ‐diaphos L2 or L9 catalyzed asymmetric hydrogenation of β ‐aryl ‐keto amides (esters), and ‐amino ketones to afford two enantiomers the desired chiral alcohols was realized with 90%‐99% yield 73%‐99% ee . This protocol could be easily conducted on gram scale in presence low catalyst loading (up 9900 TON). Moreover, hydrogenated products are versatile building blocks for a variety biologically active molecules drugs, such as Fluoxetine, Dapoxetine so on. magnified image

Language: Английский

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