Cobalt‐Catalyzed Asymmetric Aza‐Nozaki–Hiyama–Kishi (NHK) Reaction of α‐Imino Esters with Alkenyl Halides

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(7)

Опубликована: Янв. 2, 2024

Chromium-catalyzed enantioselective Nozaki-Hiyama-Kishi (NHK) reaction represents one of the most powerful approaches for formation chiral carbon-heteroatom bond. However, construction sterically encumbered tetrasubstituted stereocenter through NHK still posts a significant challenge. Herein, we disclose cobalt-catalyzed aza-NHK ketimine with alkenyl halide to provide convenient synthetic approach manufacture enantioenriched α-vinylic amino acid. This protocol exhibits excellent functional group tolerance 99 % ee in cases. Additionally, this asymmetric reductive method is also applicable aldimine access trisubstituted stereogenic centers.

Язык: Английский

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Cobalt‐Catalyzed Enantioselective Reductive α‐Chloro‐Carbonyl Addition of Ketimine to Construct the β‐Tertiary Amino Acid Analogues

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(25)

Опубликована: Янв. 22, 2024

β-Tertiary amino acid derivatives constitute one of the most frequently occurring units in natural products and bioactive molecules. However, efficient asymmetric synthesis this motif still remains a significant challenge. Herein, we disclose cobalt-catalyzed enantioselective reductive addition reaction ketimine using α-chloro carbonyl compound as radical precursor, providing expedient access to diverse array enantioenriched β-quaternary analogues. This protocol exhibits outstanding enantioselectivity broad substrate scope with excellent functional group tolerance. Preliminary mechanism studies rule out possibility Reformatsky-type confirm involvement species stereoselective process. The synthetic utility has been demonstrated through rapid assembly iterative oligopeptide, showcasing its versatile platform for late-stage modification drug candidates.

Язык: Английский

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Tetrabutylammonium decatungstate (TBADT), a compelling and trailblazing catalyst for visible-light-induced organic photocatalysis

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(19), С. 3799 - 3842

Опубликована: Янв. 1, 2024

Tetrabutylammonium decatungstate (TBADT) has recently emerged as an intriguing photocatalyst under visible-light or near-visible-light irradiation in a wide range of organic reactions that were previously not conceivable. Given its ability to absorb visible light and excellent effectiveness activating unactivated chemical bonds, it is promising addition traditional photocatalysts. This review covers some the contemporary developments photocatalysis enabled by TBADT catalyst 2023, with contents organized reaction type.

Язык: Английский

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Photo‐/Electrocatalytic Difunctionalization of Alkenes Enabled by C‐H Radical Functionalization

Chemistry - A European Journal, Год журнала: 2024, Номер 30(62)

Опубликована: Авг. 10, 2024

The difunctionalization of alkenes represents a powerful tool to incorporate two functional groups into the alkene bones for increasing molecular complexity and has been widely utilizations in chemical synthesis. Upon catalysis green, sustainable, mild photo-/electrochemistry technologies, much attentions have attracted development new tactics transformations important alkane feedstocks driven by C-H radical functionalization. Herein, we summarize recent advances photo-/electrocatalytic enabled We detailedly discuss substrate scope mechanisms reactions selecting impressive synthetic examples, which are divided four sections based on final terminated step, including oxidative radical-polar crossover coupling, reductive radical-radical transition-metal-catalyzed coupling.

Язык: Английский

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Nickel-Catalyzed Deoxygenative Amidation of Alcohols with Carbamoyl Chlorides

Organic Letters, Год журнала: 2024, Номер 26(11), С. 2297 - 2302

Опубликована: Март 11, 2024

We report a deoxygenative amidation reaction of alcohols with carbamoyl chlorides to afford amides through nickel–photoredox dual catalysis. Good excellent yields can be obtained even for diverse complex sugar and steroid derivatives. The is scalable, the synthetic utility was demonstrated by homologation deliver several important γ-amino synthetically challenging bioactive compound intermediate.

Язык: Английский

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Pd/NBE-Catalyzed One-Pot Modular Synthesis of Polycyclic Fused δ-Lactams and Investigation of Room-Temperature Phosphorescence

ACS Catalysis, Год журнала: 2024, Номер 14(16), С. 12181 - 12191

Опубликована: Июль 30, 2024

The advancement of sophisticated synthetic methodologies that streamline reaction processes while enhancing molecular complexity is a perpetual necessity in the realm chemistry. Catalytic one-pot cascade play crucial role efficient construction intricate molecules with exceptional chemoselectivity. Herein, we present approach for synthesis polycyclic fused δ-lactams via sequential phosgenation, Pd/NBE-catalyzed ortho-carbamoylation/ipso-Heck-type cyclization, and C–H activation from readily available aryl halides, amines, triphosgenes. This stands out as first example situ carbamoyl chloride formation amine precursors, presenting an alternative to existing transformations involving chlorides. practical significance these showcased by 81 rapid economically favorable manner, without need intermediate purification. Moreover, were scalable compatible various natural products pharmaceuticals, further underscoring effectiveness this strategy. relatively rigid coplanar structure displayed our synthesized exhibits distinct room-temperature phosphorescence characteristics, which have been utilized anticounterfeiting high-security-level data encryption.

Язык: Английский

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Photocatalyzed Cascade Hydrogen Atom Transfers for Assembly of Multi‐substituted α‐SCF3 and α‐SCF2H Cyclopentanones

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(34)

Опубликована: Июнь 7, 2024

A photocatalyzed formal (3+2) cycloaddition has been developed to construct original polysubstituted α-SCF

Язык: Английский

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A General Enantioselective α-Alkyl Amino Acid Derivatives Synthesis Enabled by Cobalt-Catalyzed Reductive Addition

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 12, 2024

Enantioenriched unnatural amino acids represent a prevalent motif in organic chemistry, with profound applications biochemistry, medicinal and materials science. Herein, we report cobalt-catalyzed aza-Barbier reaction of dehydroglycines unactivated alkyl halides to afford α-amino esters high enantioselectivity. This catalytic reductive alkylative addition protocol circumvents the use moisture-, air-sensitive organometallic reagents, stoichiometric chiral auxiliaries, enabling conversion variety primary, secondary, even tertiary α-alkyl-amino under mild conditions, thus leading broad functional group tolerance. The expedient access biologically active motifs demonstrates practicality this by reducing number synthetic steps enhancing efficiency.

Язык: Английский

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Nickel‐Catalyzed Regiodivergent Acylzincation of Styrenes with Organozincs and CO^†

Chinese Journal of Chemistry, Год журнала: 2023, Номер 42(6), С. 599 - 604

Опубликована: Ноя. 2, 2023

Comprehensive Summary Transition metal‐catalyzed carbometallation of unsaturated hydrocarbons constitutes one the most efficient synthetic methodologies for construction C—C bond. Recently, incorporation organometallic reagent with CO gas as a nucleophilic acyl synthon could enable acylmetallation reaction, which greatly increases horizon chemistry. Herein, we report nickel‐catalyzed regiodivergent acylzincation o ‐cyano cinnamate ester and styrene, in cyano moiety intramolecularly captures zinc intermediates to trigger tandem cyclization process. This protocol features mild conditions, broad substrate scope excellent functional group tolerance, thus affording diverse array highly functionalized carbocyclic compounds.

Язык: Английский

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Cobalt‐Catalyzed Asymmetric Aza‐Nozaki–Hiyama–Kishi (NHK) Reaction of α‐Imino Esters with Alkenyl Halides

Angewandte Chemie, Год журнала: 2024, Номер 136(7)

Опубликована: Янв. 2, 2024

Abstract Chromium‐catalyzed enantioselective Nozaki–Hiyama–Kishi (NHK) reaction represents one of the most powerful approaches for formation chiral carbon‐heteroatom bond. However, construction sterically encumbered tetrasubstituted stereocenter through NHK still posts a significant challenge. Herein, we disclose cobalt‐catalyzed aza‐NHK ketimine with alkenyl halide to provide convenient synthetic approach manufacture enantioenriched α‐vinylic amino acid. This protocol exhibits excellent functional group tolerance 99 % ee in cases. Additionally, this asymmetric reductive method is also applicable aldimine access trisubstituted stereogenic centers.

Язык: Английский

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