Chemo-, regio- and stereoselective access to polysubstituted 1,3-dienes via Nickel-catalyzed four-component reactions

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 28, 2024

1,2-Difunctionalization of alkynes offers a straightforward approach to access polysubstituted alkenes. However, simultaneous multi-component cascade transformations including difunctionalization two with both syn- and anti-selectivity in one catalyst system is undeveloped proves be significant challenge. Herein, we report Nickel-catalyzed four-component reaction 1,3-dienes using terminal alkynes, aryl boroxines, perfluoroalkyl iodides, wherein the forms three new C-C bonds single vessel serve as modular strategy excellent chemoselectivity, good regioselectivity exclusive stereoselectivity. Control experiments reveal plausible mechanism DFT calculations explain cause for formation this unusual reaction. Furthermore, successfully incorporate biologically active units into 1,2,3,4-tetrasubstituted 1,3-dienes, which greatly increases diversity molecular scaffolds brings more potential values medicinal chemistry, synthetic utility our protocol further demonstrated by late-stage transformations.

Язык: Английский

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Enantioselective Ni-Catalyzed 1,2-Borylalkynylation of Unactivated Alkenes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(25), С. 17140 - 17149

Опубликована: Июнь 12, 2024

Enantioselective three-component difunctionalization of alkenes with boron reagents represents an attractive strategy for assembling three-dimensional chiral organoboron compounds. However, regio- and enantiocontrol comprise the pivot challenges in these transformations, which predominantly require use activated conjugated alkenes. Herein, by utilizing various carbonyl directing groups, including amides, sulfinamides, ketones, esters, we succeed realizing a nickel-catalyzed 1,2-borylalkynylation unactivated to enable simultaneous incorporation entity sp-fragment across double bond. The products contain boryl, alkynyl, functional groups orthogonal synthetic reactivities, offering three handles further derivatization access valuable intermediates. utility this ligand-enabled asymmetric protocol has been highlighted through late-stage decoration drug-relevant molecules.

Язык: Английский

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Anti‐Selective Carbosilylation: Nickel‐Catalyzed Multicomponent Reaction of Solid Me₃SiZnI

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Март 28, 2024

The stereodefined and highly substituted vinylsilanes are essential building blocks for constructing complex organic molecules. Transition metal-mediated silylmetalation of alkynes was developed to overcome the limitations conventional hydrosilylations; however, a very limited study carried out utilize transient vinylmetal species in cross-coupling reactions. Moreover, they produce syn-adduct, anti-selective is still unknown desired. Silylzinc reagents functional group tolerant, their synthesis from pyrophoric silyllithium dissolved lithium salts hampers Our novel solid silylzinc circumvent these constraints employed via multi-component reaction involving Me

Язык: Английский

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New reactivity of late 3d transition metal complexes in catalytic reactions of alkynes

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review summarizes seven types of new reactivities found in late 3d metal complexes and catalytic examples recent years.

Язык: Английский

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Enantioselective Multicomponent Electrochemical Difunctionalization of Terminal Alkynes

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

Опубликована: Фев. 25, 2025

The direct functionalization of alkyne triple bonds using a radical strategy provides an efficient platform for creating wide range substituted alkenes. However, developing multicomponent enantioselective reaction feedstock alkynes to forge all-carbon quaternary stereocenters─while addressing challenges related compatibility, selectivity, and efficiency─remains relatively rare. Here we report electrochemical nickel-catalyzed three-component cross-coupling readily available terminal alkynes, diverse racemic alkyl precursors, group transfer reagents (such as (TMS)3Si-H, RSe-SeR, RTe-TeR, CHI3), achieving excellent regio-, stereo-, enantioselectivities (more than 70 examples, up 95% ee). Electricity-mediated difunctionalizations significantly expand the scope both aliphatic aromatic demonstrating functional compatibility. key success lies in rational design anodically generated nickel-bound tertiary intermediates, which stereoselectively capture form vinyl radicals participate subsequently processes enable intermolecular anti-stereoselective difunctionalization alkynes. This approach allows transformation into structural entities with α-quaternary stereogenic centers.

Язык: Английский

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Nickel‐Catalyzed Atroposelective Carbo‐Carboxylation of Alkynes with CO2: En Route to Axially Chiral Carboxylic Acids

Angewandte Chemie International Edition, Год журнала: 2024, Номер 64(1)

Опубликована: Ноя. 7, 2024

Abstract Precise synthesis of carboxylic acids via catalytic carboxylation with CO 2 is highly appealing. Although considerable advancements have been achieved in difunctionalizing unsaturated hydrocarbons, the asymmetric variants are conspicuously underdeveloped, particularly addressing axially chiral alkenes. Herein, we report first atroposelective alkynes . A variety valuable obtained good yields and high chemo‐, regio‐, Z/E enantio‐selectivities. Notably, an unexpected anti ‐selective carbo‐carboxylation observed sp ‐hybrid carbo‐electrophile‐initiated reductive alkynes. Mechanistic studies including DFT calculation elucidate origin induction ‐selectivity vinyl‐carboxylation

Язык: Английский

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Regio‐ and Diastereoselective Synthesis of Trisubstituted Alkenes Through Hydroalkylation of Alkynyl Boronamides

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Июль 8, 2024

Hydroalkylation of alkynes is a powerful method for alkene synthesis. However, regioselectivity has been difficult to achieve in transformations internal hindering applications the synthesis trisubstituted alkenes. To overcome these limitations, we explored using boryl groups as versatile directing that can control hydroalkylation and subsequently be replaced cross-coupling reaction. The result our exploration nickel-catalyzed alkynyl boronamides provides access wide range alkenes with high regio- diastereoselectivity. reaction accomplished variety coupling partners, including primary secondary alkyl iodides, α-bromo esters, α-chloro phthalimides, boronic esters. Preliminary studies mechanism provide evidence hydrometalation formation radical intermediates.

Язык: Английский

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Direct Synthesis of (E)‐β‐(Thiocyanato)vinyl Sulfones by 1,2‐Difunctionalization of Alkynes with Sulfinic Acids and Potassium Thiocyanate

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 366(3), С. 426 - 430

Опубликована: Дек. 21, 2023

Abstract A direct thiocyanatosulfonation of alkynes with sulfinic acids and potassium thiocyanate was developed at room temperature. This method provided a efficient practical pathway to selectively access ( E )‐ β ‐(thiocyanato)vinyl sulfones by two C−S bonds formation in one step under metal‐free condition. The advantages this included simple reaction conditions, easily available starting materials, good functional group compatibility, high regio‐ stereoselectivity excellent yields products.

Язык: Английский

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Anti‐Selective Carbosilylation: Nickel‐Catalyzed Multicomponent Reaction of Solid Me₃SiZnI

Angewandte Chemie, Год журнала: 2024, Номер 136(23)

Опубликована: Март 28, 2024

Abstract The stereodefined and highly substituted vinylsilanes are essential building blocks for constructing complex organic molecules. Transition metal‐mediated silylmetalation of alkynes was developed to overcome the limitations conventional hydrosilylations; however, a very limited study carried out utilize transient vinylmetal species in cross‐coupling reactions. Moreover, they produce syn‐adduct, anti‐selective is still unknown desired. Silylzinc reagents functional group tolerant, their synthesis from pyrophoric silyllithium dissolved lithium salts hampers Our novel solid silylzinc circumvent these constraints employed via multi‐component reaction involving Me 3 SiZnI, terminal alkynes, activated alkyl halides. An intensive computational experimental investigation mechanism reveals an equilibrium between intermediate syn‐ anti‐adducts; greater barrier at single electron reduction halides thermodynamic stability Ni(III) adduct determine anti‐selectivity.

Язык: Английский

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Regio‐ and Diastereoselective Synthesis of Trisubstituted Alkenes Through Hydroalkylation of Alkynyl Boronamides

Angewandte Chemie, Год журнала: 2024, Номер 136(39)

Опубликована: Июль 8, 2024

Abstract Hydroalkylation of alkynes is a powerful method for alkene synthesis. However, regioselectivity has been difficult to achieve in transformations internal hindering applications the synthesis trisubstituted alkenes. To overcome these limitations, we explored using boryl groups as versatile directing that can control hydroalkylation and subsequently be replaced cross‐coupling reaction. The result our exploration nickel‐catalyzed alkynyl boronamides provides access wide range alkenes with high regio‐ diastereoselectivity. reaction accomplished variety coupling partners, including primary secondary alkyl iodides, α‐bromo esters, α‐chloro phthalimides, boronic esters. Preliminary studies mechanism provide evidence hydrometalation formation radical intermediates.

Язык: Английский

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