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

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(37), С. 15654 - 15660

Опубликована: Авг. 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.

Язык: Английский

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Chemoselective Union of Olefins, Organohalides, and Redox-Active Esters Enables Regioselective Alkene Dialkylation

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(51), С. 21410 - 21419

Опубликована: Дек. 11, 2020

Multicomponent catalytic processes that can generate multiple C(sp3)-C(sp3) bonds in a single step under mild conditions, particularly those employ inexpensive catalysts and substrates, are highly sought-after chemistry research for complex molecule synthesis. Here, we disclose an efficient Ni-catalyzed reductive protocol chemoselectively merges alkenyl amides with two different aliphatic electrophiles. Starting materials readily accessible from stable abundant feedstock, products furnished up to >98:2 regioisomeric ratios. The present strategy eliminates the use of sensitive organometallic reagents, tolerates wide array functionalities, enables regiodivergent addition primary alkyl groups bearing similar electronic steric attributes across C═C exquisite control site selectivity. Utility is underscored by concise synthesis bioactive compounds postreaction functionalizations leading structurally diverse scaffolds. DFT studies revealed regiochemical outcome originates orthogonal reactivity chemoselectivity profiles situ generated organonickel species.

Язык: Английский

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Three-component 1,2-dicarbofunctionalization of alkenes involving alkyl radicals

Chemical Communications, Год журнала: 2021, Номер 58(6), С. 730 - 746

Опубликована: Дек. 8, 2021

This article provides a comprehensive perspective on three-component 1,2-dicarbofunctionalization of alkenes involving alkyl radicals, which generated from structurally diverse electrophilic and nucleophilic precursors under mild conditions.

Язык: Английский

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General method for iron-catalyzed multicomponent radical cascades–cross-couplings

Science, Год журнала: 2021, Номер 374(6566), С. 432 - 439

Опубликована: Окт. 22, 2021

Iron links a trio holds particular appeal as catalytic metal—it is safe and abundant, well mainstay of enzymatic reactivity. Nonetheless, in synthetic construction carbon-carbon bonds, modern chemists have largely had to rely on rarer metals such palladium. Liu et al . now report that coordination iron by bulky chelating phosphine ligand enables efficient mutual coupling three different reactants—an alkyl halide, an aryl Grignard, olefin—to form two bonds (see the Perspective Lefèvre). A combination Mössbauer spectroscopy, crystallography, computational simulations illuminates mechanism. —JSY

Язык: Английский

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Cu-Catalyzed Enantioselective Alkylarylation of Vinylarenes Enabled by Chiral Binaphthyl–BOX Hybrid Ligands

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(45), С. 19017 - 19022

Опубликована: Окт. 5, 2020

Transition-metal-catalyzed radical relay coupling reactions have recently emerged as one of the most powerful methods to achieve difunctionalization olefins. However, there has been limited success in applying this method asymmetric catalysis using an effective chiral ligand. Herein we report Cu-catalyzed enantioselective alkylarylation vinylarenes alkylsilyl peroxides alkyl sources. This reaction proceeds under practical conditions and affords 1,1-diarylalkane structures that are found a variety bioactive molecules. Notably, highly was accomplished by combining bis(oxazoline) ligands with binaphthyl scaffolds.

Язык: Английский

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