Facile Access to Quaternary Carbon Centers via Ni-Catalyzed Arylation of Alkenes with Organoborons

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 16, 2025

Quaternary carbon centers are widespread structural motifs, thus representing extensive interest in organic synthesis. We describe here an efficient nickel-catalyzed intermolecular, Markovnikov-selective arylation of minimally functionalized alkenes with stable organoborons, affording a broad range cyclic or acyclic quaternary under mild conditions. The utilization the diimine ligand is critical for high reactivity and chemoselectivity. Furthermore, using bulky chiral as Ni catalyst, stereocenters can be readily prepared levels enantiocontrol. Mechanism studies suggest that, before protonation, rare nickel shift from alkyl to aryl might occur.

Язык: Английский

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Copper-Catalyzed Yne-Allylic Substitutions Using Stabilized Nucleophiles

ACS Catalysis, Год журнала: 2022, Номер 12(12), С. 6840 - 6850

Опубликована: Май 25, 2022

Using stabilized "soft" nucleophiles in copper-catalyzed allylic substitutions is highly desirable but remains an unsolved challenge for the last 40 years. In this work, a general protocol of using such as indoles, pyrroles, amines, and 1,3-dicarbonyls has been developed, delivering large variety functionalized 1,3- 1,4-enynes with high levels regio- stereoselectivities (67 examples). A range further transformations products can be easily achieved to release various molecules. mechanistic rationale copper acetylide-bonded cation key intermediate that features outer-sphere nucleophilic attack proposed. Additionally, series diversified reactivities have demonstrated, which will inspire studies.

Язык: Английский

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Cobalt-Catalyzed Diastereo- and Enantioselective Carbon–Carbon Bond Forming Reactions of Cyclobutenes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(6), С. 3588 - 3598

Опубликована: Фев. 3, 2023

Catalytic enantioselective functionalization of cyclobutenes constitutes a general and modular strategy for construction enantioenriched complex cyclobutanes bearing multiple stereogenic centers, as chiral four-membered rings are common motifs in biologically active molecules versatile intermediates organic synthesis. However, synthesis through such remained significantly limited. Herein, we report series unprecedented cobalt-catalyzed carbon-carbon bond forming reactions that initiated carbometalation. The protocols feature diastereo- introduction allyl, alkynyl, functionalized alkyl groups. Mechanistic studies indicated an unusual 1,3-cobalt migration subsequent β-carbon elimination cascade process occurred the allyl addition. These new discoveries established elementary cobalt catalysis extension diversity nucleophiles transformations cyclobutenes.

Язык: Английский

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Nickel-Catalyzed Carbonylation of Cyclopropanol with Benzyl Bromide for Multisubstituted Cyclopentenone Synthesis

Organic Letters, Год журнала: 2022, Номер 24(14), С. 2699 - 2704

Опубликована: Апрель 7, 2022

Herein, we reported a Ni-catalyzed carbonylation of cyclopropanol with benzyl bromide to afford multisubstituted cyclopentenone under 1 atm CO. The reaction proceeds through cascade bromides, followed by generation nickel homoenolate from cyclopropanols via β-C elimination 1,4-diketones, which undergoes intramolecular Aldol condensation furnish highly substituted derivatives in moderate good yields. exhibits high functional group tolerance broad substrate scope.

Язык: Английский

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Copper-catalyzed asymmetric allylic substitution of racemic/meso substrates

Chemical Science, Год журнала: 2024, Номер 15(22), С. 8280 - 8294

Опубликована: Янв. 1, 2024

The synthesis of enantiomerically pure compounds is a pivotal subject in the field chemistry, with enantioselective catalysis currently standing as primary approach for delivering specific enantiomers. Among these strategies, Cu-catalyzed asymmetric allylic substitution (AAS) significant and irreplaceable, especially when it comes to use non-stabilized nucleophiles (pK > 25). Although AAS prochiral substrates has also been widely developed, methodologies involving racemic/meso are highly desirable, undergo dynamic processes give single enantiomer products. Inspired by pioneering work Alexakis, Feringa Gennari groups, continuously employed deracemization desymmetrization enriched In this review, we mainly focus on developments over past two decades, providing an explicit outline ligands employed, scope nucleophiles, underlying their practical applications.

Язык: Английский

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Ring‐Opening Cross‐Coupling/Cyclization Reaction of Cyclopropanols with Organic Compounds

ChemistrySelect, Год журнала: 2023, Номер 8(32)

Опубликована: Авг. 23, 2023

Abstract Cyclopropanols, due to their particular chemistry, can participate in various synthetic reactions with retention or cleavage of the strained three‐membered ring. Direct cross‐coupling ring‐opening reaction such molecules access organic compounds, as ketones has great importance medicinal chemistry and material sciences. Hence, coupling reaction/cyclization cyclopropanols for constructing new valuable presence a transition metal catalyst under metal‐free conditions is described this context. The features are discussed, mechanisms challenging highlighted.

Язык: Английский

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Visible-light-induced tandem ring opening/1,6-conjugate addition of cyclobutanols with p-quinone methides under metal- and additive-free conditions

Green Chemistry, Год журнала: 2024, Номер 26(3), С. 1375 - 1380

Опубликована: Янв. 1, 2024

A visible-light-mediated tandem ring opening/1,6-conjugate addition of cyclobutanols with p -quinone methides was developed. This protocol allowed the formation δ,δ-diaryl ketones in presence a readily available organic photocatalyst.

Язык: Английский

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Synthesis of pyranopyrazoles with a chiral quaternary carbon stereocenter via copper-catalyzed enantioselective [3 + 3] cycloaddition

Chemical Communications, Год журнала: 2022, Номер 58(17), С. 2850 - 2853

Опубликована: Янв. 1, 2022

A copper-catalyzed enantioselective [3 + 3] cycloaddition of propargyl carbonates and pyrazolones has been disclosed. This reaction provided an efficient route to synthesize pyranopyrazoles containing a chiral quaternary carbon stereocenter in good yields with excellent enantioselectivities. In addition, the hydroxyl group products could be conveniently transformed into variety functional groups, such as aldehyde, nitrile, alkene, ester amide which further increased synthetic value this reaction.

Язык: Английский

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Recent Advances in Non-Precious Metal Catalysis

Organic Process Research & Development, Год журнала: 2022, Номер 26(8), С. 2281 - 2310

Опубликована: Авг. 2, 2022

This review provides a summary of recently published developments in the field nonprecious metal catalysis (NPMC) and highlights range synthetic applications captured research between July October 2021. is an installment series on this area briefing Ni, Cu, Fe, Co catalysis. There has been evident increase publications NPMC, which indicates widespread interest among laboratories academia industry development utilization catalytic these metals.

Язык: Английский

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Arylation of Cyclopropanol with Pyrrole: Asymmetric Synthesis of Indolizidine 167B, Indolizidine 209D, and Monomorine I

Organic Letters, Год журнала: 2023, Номер 25(12), С. 2058 - 2062

Опубликована: Март 17, 2023

A Fe(NO3)3-mediated ring-opening arylation of cyclopropanol with the electron-rich pyrrole has been developed, which might proceed through oxidative radical ring opening followed by cyclization to motif and then aromatization. This method enables direct without prefunctionalization thus allows rapid access a diverse array chiral 5,6,7,8-tetrahydroindolizines from easily available amino acid esters. The synthetic utility demonstrated asymmetric synthesis alklaoids (-)-indolizidine 167B, (+)-indolizidine 209D, (+)-monomorine I, natural product analogue.

Язык: Английский

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