Iron- and Cobalt-Catalyzed Asymmetric Hydrofunctionalization of Alkenes and Alkynes

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(11), P. 2701 - 2716

Published: May 20, 2021

ConspectusTransition metal catalyzed asymmetric hydrofunctionalization of readily available unsaturated hydrocarbons presents one the most straightforward and atom-economic protocols to access valuable optically active products. For decades, noble transition catalysts have laid cornerstone in this field, on account their superior reactivity selectivity. In recent years, from an economical sustainable standpoint, first-row, earth-abundant metals received considerable attention, due high natural reserves, affordable costs, low toxicity. Meanwhile, reactions also gained much interest been investigated gradually. However, since chiral ligand libraries for transition-metal catalysis are limited date, development highly enantioselective versions remains a significant challenge.This Account summarizes our efforts developing suitable ligands iron cobalt applications (hydroboration hydrosilylation) alkenes alkynes. design, we envisioned that unsymmetric NNN-tridentate (UNT) scaffolds could promote these transformations with metals. Therefore, several types UNT were designed prepared laboratory, utilizing amino acids as sources. very beginning, oxazoline iminopyridine (OIP) proposed through rational combination nitrogen-containing scaffolds. After systematic survey effects, imine moiety rigid OIP was replaced by conformationally more flexible amine unit, leading construction reactive aminoisopropylpyridine (OAP) ligands. Subsequently, imidazoline (IIP) thiazoline (TIP) altering oxygen atom nitrogen sulfur linkers, respectively. To further expand library, other tridentate containing twisted pincer, anionic, nonrigid backbone synthesized, including iminophenyl oxazolinyl phenylamine (IPOPA) phenyl picolinamide (ImPPA). The efficacy induction has demonstrated sequential alkynes, which exhibit excellent well chemo-, regio-, stereoselectivity broad functional group tolerance. Notably, regio- challenging substrates, such 1,1-disubstituted aryl terminal aliphatic alkenes, achieved. Furthermore, isomerization/hydroboration internal alkynes demonstrates synthetic power catalytic systems. enantioenriched products obtained methodologies be potentially utilized organic synthesis, medicinal chemistry, materials science. We believe continuous field would beneficial catalysis.

Language: Английский

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The transition metal-catalysed hydroboration reaction

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(21), P. 8877 - 8922

Published: Jan. 1, 2022

This review covers the development of transition metal-catalysed hydroboration reaction, from its beginnings in 1980s to more recent developments including earth-abundant catalysts and an ever-expanding array substrates.

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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P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(14), P. 8657 - 8739

Published: July 2, 2024

Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality and P-stereogenic ligands. Most reported belong to former class. Privileged ones such as BINAP DuPhos frequently employed wide range catalytic transformations. In contrast, latter class has remained small family many years mainly because their synthetic difficulty. The late 1990s saw emergence novel with superior enantioinduction ability Rh-catalyzed hydrogenation reactions. Since then, numerous have been synthesized used This Review summarizes thus far, including stereochemical electronic properties that afford high excellent enantioselectivities. Examples reactions use this described together applications construction key intermediates natural products therapeutic agents. literature covered dates back 1968 up until December 2023, centering on studies published later years.

Language: Английский

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Cobalt-Catalyzed Enantioselective Hydroarylation of 1,6-Enynes

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(20), P. 9510 - 9517

Published: April 25, 2020

An asymmetric hydroarylative cyclization of enynes involving a C–H bond cleavage is reported. The cobalt-catalyzed cascade generates three new bonds in an atom-economical fashion. products were obtained excellent yields and enantioselectivities as single diastereo- regioisomers. Preliminary mechanistic studies indicate that the reaction shows no intermolecular crossover. This work highlights potential cobalt catalysis functionalization enantioselective domino reactivity.

Language: Английский

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Quinim: A New Ligand Scaffold Enables Nickel-Catalyzed Enantioselective Synthesis of α-Alkylated γ-Lactam

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(37), P. 15654 - 15660

Published: Aug. 26, 2020

Herein, we report a nickel-catalyzed reductive cross-coupling reaction of easily accessible 3-butenyl carbamoyl chloride with primary alkyl iodide to access the chiral α-alkylated pyrrolidinone broad substrate scope and high enantiomeric excess. The current art synthesis still remains challenging on enantioselective α-monoalkylation pyrrolidinones. newly designed 8-quinoline imidazoline ligand (Quinim) is crucial for maintaining reactivity enantioselectivity ensure cyclization monosubstituted alkenes unprecedented non-aromatic heterocycles.

Language: Английский

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Stereodivergent Synthesis through Catalytic Asymmetric Reversed Hydroboration

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(11), P. 4670 - 4677

Published: Feb. 26, 2019

The control of chemo-, regio-, diastereo-, and enantioselectivity is a central theme in organic synthesis. capability to obtain the full set stereoisomers molecule would significantly enhance efficiency for synthesis natural product analogues creation chiral compound libraries drug discovery. Despite tremendous progress achieved field asymmetric past decades, precise both relative absolute configurations catalyst-controlled reactions that create multiple stereocenters remains significant synthetic challenge. We report here development hydroboration with hitherto unattainable selectivity. Rh-catalyzed α, β-unsaturated carbonyl compounds pinacolborane proceeds high levels enantioselectivities provide two vicinal stereocenters. Through appropriate choice substrate geometry (E or Z) ligand enantiomer (S R), all possible diastereoisomers are readily accessible. boron-containing products underwent many stereospecific transformations, thus providing strategy collective stereodivergent diverse valuable building blocks.

Language: Английский

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Cobalt-Catalyzed Enantioselective and Chemodivergent Addition of Cyclopropanols to Oxabicyclic Alkenes

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(6), P. 5638 - 5644

Published: May 22, 2019

We report herein cobalt-catalyzed enantioselective and chemodivergent reactions between a cyclopropanol an oxabicyclic alkene via cobalt homoenolate, which afford either alkylative ring-opening product or hydroalkylation product, with the counterion of catalyst being major chemoselectivity-controlling factor. A generated from cobalt(II) chloride chiral diphosphine promotes ring opening to 1,2-dihydronaphthalen-1-ol derivatives in good yields high enantioselectivity. By contrast, acetate same ligand, assistance methanol, selectively affords products retention bicyclic structure at comparable level

Language: Английский

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Versatile cobalt-catalyzed regioselective chain-walking double hydroboration of 1,n-dienes to access gem-bis(boryl)alkanes

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: Feb. 7, 2020

Abstract Double hydroboration of dienes is the addition a hydrogen and boryl group to two double bonds diene molecule represents straightforward effective protocol prepare synthetically versatile bis(boryl)alkanes, provided that this reaction occurs selectively. However, can potentially yield several isomeric organoboron products, it still remains challenge control regioselectivity reaction, which allows selective production single product, in particular, for broad scope dienes. By employing readily available cobalt catalyst, here we show yields useful gem -bis(boryl)alkanes with excellent regioselectivity. In addition, encompasses wide range conjugated non-conjugated Furthermore, mechanistic studies indicate cobalt-catalyzed through boryl-directed chain-walking alkenylboronates generated from anti -Markovnikov 1,2-hydroboration 1,n-diene.

Language: Английский

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Hydroelementation of diynes

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(3), P. 869 - 994

Published: Jan. 1, 2022

This review highlights the hydroelementation reactions of conjugated and separated diynes, which depending on process conditions, catalytic system, as well type reagents, leads to formation various products: enynes, dienes, allenes, polymers, or cyclic compounds. The presence two triple bonds in diyne structure makes these compounds important reagents but selective product is often difficult owing problems associated with maintaining appropriate reaction regio- stereoselectivity. Herein we this topic gain knowledge reactivity diynes systematise range information relating their use reactions. divided according addition E-H (E = Mg, B, Al, Si, Ge, Sn, N, P, O, S, Se, Te) bond bond(s) diyne, reagent used, formed. Not only are comprehensively discussed, synthetic potential obtained products also presented. majority published research included within review, illustrating limitations processes, intent showcase power transformations synthesis materials chemistry.

Language: Английский

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