First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(21), P. 13238 - 13341

Published: Oct. 7, 2021

Organoboron reagents represent a unique class of compounds because their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation the carbon–boron bond into carbon–X (X = C, N, and O) stereocontrolled fashion has become invaluable medicinal agrochemistry, natural products chemistry as well materials science. Over past decade, first-row d-block transition metals have increasingly widely used catalysts for formation bond, traditionally catalyzed by expensive precious metals. This recent focus on alternative enabled growth fundamental methods organoboron chemistry. review surveys current state-of-the-art use element-based bonds.

Language: Английский

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Asymmetric hydrogenation catalyzed by first-row transition metal complexes

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(5), P. 3211 - 3237

Published: Jan. 1, 2021

This review focuses on asymmetric direct and transfer hydrogenation with first-row transition metal complexes. The reaction mechanisms the models of enantiomeric induction were summarized emphasized.

Language: Английский

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Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(13), P. 6124 - 6196

Published: June 3, 2020

A critically important process in catalysis is the formation of an active catalyst from combination a metal precursor and ligand, as efficacy this reaction governs amount catalyst. This Review comprehensive overview reactions catalyzed by nickel added bidentate phosphine, focusing on steps transforming precatalyst ligand into potential effects transformation catalysis. Reactions covered include common cross-coupling reactions, such Suzuki, Heck, Kumada, Negishi couplings, addition cycloadditions, C–H functionalizations, polymerizations, hydrogenations, reductive among others. Overall, most widely used with free phosphines Ni(cod)2, which accounts for ∼50% reports surveyed, distantly followed Ni(acac)2 Ni(OAc)2, account ∼10% each. By compiling these we have calculated statistics usage each Ni(cod)2 other sources. The are simple, relatively inexpensive ligands, DPPE, DCPE, DPPP, DPPB, along others more complex backbones, DPPF Xantphos. use expensive chiral scattered, but ligands BINAP, Me-Duphos, Josiphos, related analogs.

Language: Английский

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Enantioselective formation of quaternary carbon stereocenters in natural product synthesis: a recent update

Natural Product Reports, Journal Year: 2019, Volume and Issue: 37(2), P. 276 - 292

Published: Sept. 13, 2019

The enantioselective formation of quaternary carbon stereocenters in complex natural product synthesis the latest six years is reviewed, with particular emphasis on analysis stereochemical model each transformation.

Language: Английский

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Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(18), P. 10672 - 10714

Published: Aug. 14, 2020

Enantioselective transition metal catalysis is an area very much at the forefront of contemporary synthetic research. The development processes that enable efficient synthesis enantiopure compounds unquestionable importance to chemists working within many diverse fields central science. Traditional approaches solving this challenge have typically relied on leveraging repulsive steric interactions between chiral ligands and substrates in order raise energy one diastereomeric states over other. By contrast, Review examines alternative tactic which a set attractive noncovalent operating are used control enantioselectivity. Examples where creative approach has been successfully applied render fundamental enantioselective presented discussed. In cases examined, ligand scaffold carefully designed accommodate these interactions, while others, critical was only elucidated subsequent computational mechanistic studies. Through exploration discussion recent reports encompassing wide range reaction classes, we hope inspire continue develop asymmetric transformations based powerful concept.

Language: Английский

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Asymmetric Synthesis of P-Stereogenic Secondary Phosphine-Boranes by an Unsymmetric Bisphosphine Pincer-Nickel Complex

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(15), P. 5685 - 5690

Published: April 9, 2021

The first highly enantioselective catalytic synthesis of P-stereogenic secondary phosphine-boranes was realized by the asymmetric addition primary phosphine to electron-deficient alkenes with a newly developed unsymmetric bisphosphine (PCP′) pincer-nickel complex. Various were obtained in 57–92% yields up 99% ee and >20:1 dr. follow-up alkylation upon P–C bond formation alkyl halides provided practical way access P-chiral compounds diverse functional groups.

Language: Английский

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Ni-Catalyzed Asymmetric Hydrophosphination of Unactivated Alkynes

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(30), P. 11309 - 11316

Published: July 20, 2021

The practical synthesis of P-stereogenic tertiary phosphines, which have wide applications in asymmetric catalysis, materials, and pharmaceutical chemistry, represents a significant challenge. A regio- enantioselective hydrophosphination using cheap ubiquitous alkynes catalyzed by nickel complex was designed, the toxic air-sensitive secondary phosphines were prepared situ from bench-stable phosphine oxides. This methodology has been demonstrated with unprecedented substrate scope functional group compatibility to afford electronically structurally diversified P(III) compounds. products could be easily converted into various precursors bidentate ligands organocatalysts, as well variety transition-metal complexes containing both P- metal-stereogenic centers.

Language: Английский

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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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Palladium-catalyzed asymmetric hydrophosphination of internal alkynes: Atroposelective access to phosphine-functionalized olefins

Chem, Journal Year: 2022, Volume and Issue: 8(12), P. 3346 - 3362

Published: Sept. 23, 2022

Language: Английский

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Modular and Facile Access to Chiral α-Aryl Phosphates via Dual Nickel- and Photoredox-Catalyzed Reductive Cross-Coupling

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(9), P. 3989 - 3997

Published: Feb. 22, 2022

Chiral phosphine-containing skeletons are important motifs in bioactive natural products, pharmaceuticals, chiral catalysts, and ligands. Herein, we report a general modular platform to access α-aryl phosphorus compounds via Ni/photoredox-catalyzed enantioconvergent reductive cross-coupling between α-bromophosphates aryl iodides. This dual catalytic regime exhibited high efficiency good functional group compacity. A wide variety of substrates bearing diverse set groups could be converted into phosphates excellent yields enantioselectivities. The utility the method was also demonstrated by development new phosphine ligand synthesis enzyme inhibitor derivatives. detailed mechanistic studies supported radical chain process revealed unique distinction compared with traditional cross-coupling.

Language: Английский

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