Palladium-catalyzed enantioselective carbonylation reactions

Science China Chemistry, Journal Year: 2022, Volume and Issue: 65(3), P. 441 - 461

Published: Jan. 5, 2022

Abstract Carbonylation, one of the most powerful approaches to preparation carbonylated compounds, has received significant attention from researchers active in various fields. Indeed, impressive progress been made on this subject over past few decades. Among types carbonylation reactions, asymmetric is a straightforward methodology for constructing chiral compounds. Although rhodium-catalyzed enantioselective hydroformylations have discussed several elegant reviews, general review palladium-catalyzed carbonylations still missing. In review, we summarize and discuss recent achievements reactions. Notably, review’s contents are categorized by reaction type.

Language: Английский

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Catalytic Asymmetric Hydroalkoxylation and Formal Hydration and Hydroaminoxylation of Conjugated Dienes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 3915 - 3925

Published: Feb. 10, 2023

The straightforward construction of stereogenic centers bearing unprotected functional groups, as in nature, has been a persistent pursuit synthetic chemistry. Abundant applications free enantioenriched allyl alcohol and hydroxylamine motifs have made the asymmetric hydration hydroaminoxylation conjugated dienes from water hydroxylamine, respectively, intriguing efficient routes that have, however, unachievable thus far. A fundamental challenge is failure to realize transition-metal-catalyzed enantioselective C–O bond constructions via hydrofunctionalization dienes. Here, we perform comprehensive study toward stereoselective formal by synthesizing set new P,N-ligands identifying an aryl-derived oxime surrogate for both hydroxylamine. Asymmetric hydroalkoxylation with also elucidated. Furthermore, versatile derivatizations following provide indirect but concise hydrophenoxylation, hydrofluoroalkoxylation, hydrocarboxylation unreported Finally, ligand-to-ligand hydrogen transfer process proposed based on results preliminary mechanistic experiments.

Language: Английский

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Cobalt-catalyzed synthesis of amides from alkenes and amines promoted by light

Science, Journal Year: 2024, Volume and Issue: 383(6678), P. 77 - 81

Published: Jan. 4, 2024

Catalytic methods to couple alkene and amine feedstocks are valuable in synthetic chemistry. The direct carbonylative coupling of alkenes amines holds promise as a perfectly atom-economical approach amide synthesis, but general remain underdeveloped. Herein, we report an hydroaminocarbonylation catalyzed by unmodified, inexpensive cobalt carbonyl under mild conditions low pressure promoted light. Silane addition after the reaction enables sequential cobalt-catalyzed reduction, constituting formal hydroaminomethylation. These exhibit exceptional scope across both components with high chemo- regioselectivity proceed efficiently even absence solvent. formation hydridocobalt through photodissociation ligand is proposed enable catalytic activity conditions, which addresses long-standing challenge catalysis.

Language: Английский

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Palladium-Catalyzed Difluorocarbene Transfer Enabled Divergent Synthesis of γ-Butenolides and Ynones from Iodobenzene and Terminal Alkynes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1722 - 1731

Published: Jan. 4, 2024

Herein, we report a ligand-controlled palladium-catalyzed method that enables the synthesis of ynones and γ-butenolides with excellent regioselectivity from same set readily available aryl iodides, acetylenes, BrCF2CO2K. In this reaction, [PdII]═CF2 does demonstrate electrophilicity can generate CO when reacting H2O. It is environmentally friendly safe compared to traditional methods, current protocol us afford in high yields functionality tolerance. Moreover, esters also be obtained corresponding phenols alcohols utilizing strategy. The success late-stage functionalization bioactive compounds further illustrates synthetic utility material development drug discovery.

Language: Английский

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Palladium-Catalyzed Markovnikov Hydroaminocarbonylation of 1,1-Disubstituted and 1,1,2-Trisubstituted Alkenes for Formation of Amides with Quaternary Carbon

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(19), P. 7298 - 7305

Published: May 10, 2021

Hydroaminocarbonylation of alkenes is one the most promising yet challenging methods for synthesis amides. Herein, we reported development a novel and effective Pd-catalyzed Markovnikov hydroaminocarbonylation 1,1-disubstituted or 1,1,2-trisubstituted with aniline hydrochloride salts to afford amides bearing an α quaternary carbon. The reaction makes use readily available starting materials, tolerates wide range functional groups, provides facile straightforward approach diverse array Mechanistic investigations suggested that proceeded through palladium hydride pathway. hydropalladation CO insertion are reversible, aminolysis probably rate-limiting step.

Language: Английский

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Palladium‐Catalyzed Asymmetric Markovnikov Hydroxycarbonylation and Hydroalkoxycarbonylation of Vinyl Arenes: Synthesis of 2‐Arylpropanoic Acids

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(43), P. 23117 - 23122

Published: July 9, 2021

Abstract Asymmetric hydroxycarbonylation is one of the most fundamental yet challenging methods for synthesis carboxylic acids. Herein, we reported development a palladium‐catalyzed highly enantioselective Markovnikov vinyl arenes with CO and water. A monodentate phosphoramidite ligand L6 plays vital role in reaction. The reaction tolerates range functional groups, provides facile atom‐economical approach to an array 2‐arylpropanoic acids including several commonly used non‐steroidal anti‐inflammatory drugs. catalytic system has also enabled asymmetric hydroalkoxycarbonylation alcohols afford 2‐arylpropanates. Mechanistic investigations suggested that hydropalladation irreversible regio‐ enantiodetermining step, while hydrolysis/alcoholysis probably rate‐limiting step.

Language: Английский

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Nickel‐Catalyzed Asymmetric Hydroaryloxy‐ and Hydroalkoxycarbonylation of Cyclopropenes

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: July 15, 2022

Abstract The asymmetric Reppe carbonylation reactions provide a straightforward access to α ‐chiral carbonyl compounds. reported paradigms predominantly adopted precious palladium as the catalyst. Here we report nickel‐catalyzed of cyclopropenes with phenyl formate and CO/ROH, respectively. This asymmetrical synthetic protocol features high atom economy, good functional group tolerance, which rapidly constructs polysubstituted cyclopropanecarboxylic derivatives excellent diastereo‐ enantioselectivity. utility is demonstrated by facile conversion chiral products into bioactive molecules such (−)‐Tranylcypromine (−)‐Lemborexant.

Language: Английский

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Progress on transition metal catalyzed asymmetric hydroesterification, hydrocarboxylation, and hydroamidation reactions of olefins

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(15), P. 6757 - 6773

Published: Jan. 1, 2022

Hydrocarboxylation, hydroesterification, and hydroamidation of olefins are fundamental transformations in organic synthesis. Asymmetric processes for these provide an effective straightforward approach to optically active carboxylic acids their derivatives, which highly useful compounds pharmaceuticals, materials, fine chemicals, etc. This review provides a brief summary the development asymmetric hydrocarboxylation, with CO its surrogates.

Language: Английский

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Regioselective and Enantioselective Copper‐Catalyzed Hydroaminocarbonylation of Unactivated Alkenes and Alkynes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: Aug. 16, 2023

Given the prevalence of amide backbones in marketed pharmaceuticals and their ubiquity as critical binding units natural peptides proteins, it remains important to develop novel methods construct bonds. We report here a general method for anti-Markovnikov hydroaminocarbonylation unactivated alkenes under mild conditions, using copper catalysis combination with hydroxylamine electrophile reagents poly(methylhydrosiloxane) (PMHS) cheap environmentally friendly hydride source. The reaction tolerates variety functional groups efficiently converts terminal alkenes, 1,1-disubstituted cyclic corresponding amides exclusive selectivity (and high enantioselectivities/diastereoselectivities). Additionally, minimal modification alkynes can also undergo tandem hydrogenation-hydroaminocarbonylation alkyl amides.

Language: Английский

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Palladium‐Catalyzed Inward Isomerization Hydroaminocarbonylation of Alkenes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(26)

Published: April 15, 2024

In contrast to the kinetically favored outward isomerization-hydrocarbonylation of alkenes, disfavored inward alkenes remains an important challenge. Herein, we have developed a novel and effective palladium-catalyzed isomerization-hydroaminocarbonylation unactivated aniline hydrochlorides for formation synthetically valuable α-aryl carboxylic amides in high yields site-selectivities. The efficiency reaction is attributed relay catalysis strategy, which Markovnikov-favored [PdH]-P

Language: Английский

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