Ligand-controlled stereodivergent alkenylation of alkynes to access functionalized trans- and cis-1,3-dienes

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Jan. 4, 2023

Precise stereocontrol of functionalized alkenes represents a long-standing research topic in organic synthesis. Nevertheless, the development catalytic, easily tunable synthetic approach for stereodivergent synthesis both E-selective and even more challenging Z-selective highly substituted 1,3-dienes from common substrates remains underexploited. Here, we report photoredox nickel dual catalytic strategy sulfonylalkenylation terminal alkynes with vinyl triflates sodium sulfinates under mild conditions. With judicious choice simple catalyst ligand, this method enables efficient divergent access to Z- E-sulfonyl-1,3-dienes same set starting materials. This features broad substrate scope, good functional compatibility, excellent chemo-, regio-, stereoselectivity. Experimental DFT mechanistic studies offer insights into observed stereoselectivity controlled by ligands.

Language: Английский

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Transition‐Metal‐Mediated Fluoroalkylation of Carbon Electrophiles through Cross‐Electrophile Couplings

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 1, 2024

Comprehensive Summary Organofluorine compounds have attracted substantial interest in life and materials sciences due to the unique properties of fluorine atom(s) that often change physicochemical biological organic molecules. Transition‐metal‐mediated cross‐electrophile coupling between carbon electrophiles fluoroalkyl has emerged as a straightforward efficient route for synthesis wide range fluoroalkylated because its synthetic convenience without tedious organometallic reagents. Moreover, alkenes or alkynes‐involved three‐component couplings provide rapid effective access carbonfunctionalized alkanes alkenes. Herein, we comprehensively summarize transition‐metal‐mediated reductive fluoroalkylation diverse through historical perspective, including trifluoromethylation, difluoroalkylation, monofluoroalkylation, so on. Different transition metals (Cu, Ni, etc .) strategies are discussed, which nickel‐catalyzed reactions represent an attractive site‐selectively organofluorine compounds. Key Scientists As early 1965, McLoughlin Thrower finished first stoichiometric copper‐mediated aromatic iodides with iodides. However, excess elevated temperature were used this method. In 1969, Kobayashi Kumadaki reported studies on trifluoromethylation halides trifluoromethyl iodide. After more than four decades, Zhang group developed β ‐fluorinated alkylation (hetero)aryl secondary alkyl bromides 2015, difluoromethylation chlorides chlorodifluoromethane ClCF 2 H 2017. The also enantioselective alkyl‐arylation 3,3,3‐trifluoropropene tertiary 2018, MacMillan novel copper/photoredox dual catalytic system aryl ( S )‐(trifluoromethyl) dimesitylsulfonium triflate presence tris‐(trimethylsilyl) silanol. They nickel/photoredox catalyzed silane. During time, Wang monofluoroalkylation monofluoroalkyl halides. From 2021 2023, same further series trifluoroalkylation aryl, alkenyl, acyl nonfluorinated alkynes could be couplings. Chu fluoroalkyl‐acylation Later, they fluoroalkyl‐arylation unactivated tethering pendant chelating group. 2019, Chaładaj palladium‐catalyzed perfluoroalkyl‐arylation perfluoroalkyl

Language: Английский

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Stereospecific Assembly of Trisubstituted Alkenes via Photoinduced Nitrogen‐Centered Radical‐Triggered C—C Bond Cleavage/Functionalization of Oxime Esters

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(12), P. 1399 - 1406

Published: Feb. 29, 2024

Comprehensive Summary A general and convenient photoredox‐catalyzed acylation alkylcyanation of MBH acetates has been established, enabling the assembly C(sp 2 )–C(sp 3 ) bond by a nitrogen‐centered radical strategy for synthesis trisubstituted alkenes in moderate to excellent chemical yields (48 examples total). The reaction with acyl (indanone) oxime esters afforded containing 1,4‐dicarbonyl groups. Interestingly, use Eosin Y as photocatalyst catalytic system resulted formation distal cyano group‐anchored via deconstructive functionalization cycloketone esters. Notably, these resulting compounds could be applied late‐stage transformations, providing important methods dihydropyridazin‐3(2 H )‐one.

Language: Английский

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Difluoroalkylative carbonylation of alkenes to access carbonyl difluoro-containing heterocycles: convenient synthesis of gemigliptin

Science China Chemistry, Journal Year: 2022, Volume and Issue: 66(1), P. 139 - 146

Published: Dec. 12, 2022

Abstract Fluorinated heterocycles play a vital role in pharmaceutical and agrochemical industries. Hence, rapid efficient construction of fluorinated remains highly demanded. Herein, difluoroalkylative carbonylative cyclization unactivated alkenes ethylene gas enabled by palladium catalysis has been developed for the first time toward synthesis α-carbonyl difluoro-modified glutarimides. This procedure can also be applied to GeMigliptin which is medicine approved treatment type 2 diabetes mellitus.

Language: Английский

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Recent Progress in Transition-Metal-Catalyzed Reductive Cross-Coupling Reactions Using Diboron Reagents as Reductants

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(23), P. 15469 - 15480

Published: Nov. 16, 2023

Transition-metal-catalyzed reductive cross-coupling reactions have been developed as one of the important tools for constructing C–C bonds. These involve direct coupling two distinct electrophiles promoted by transition metals and reductants. Notably, these methods offer advantages over conventional because they circumvent need air- moisture-sensitive organometallic reagents while being simple to operate exhibiting good compatibility with various functional groups. In recent years, diboron gained prominence reductants alongside traditional metal reductants, such Zn, Mn, Mg. This Review aims provide an insightful overview nickel/copper/iron-catalyzed using illustrate their possible reaction mechanisms.

Language: Английский

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Nickel-Catalyzed Asymmetric Cross-Electrophile trans-Aryl-Benzylation of α-Naphthyl Propargylic Alcohols

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(10), P. 6795 - 6803

Published: May 3, 2023

Herein, we report a nickel-catalyzed asymmetric three-component trans-dicarbofunctionalization of β-substituted α-naphthyl propargylic alcohols using readily available aryl and benzyl halides as the coupling partners under reductive conditions. This cross-electrophile strategy enables synthesis various axially chiral allylic bearing tetrasubstituted olefinic unit in complete regio- E selectivity, well high enantiocontrol. Relying on hydroxyl group functional handle, such structural motifs are successfully derivatized into diverse functional-group-rich alkenes.

Language: Английский

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

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 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.

Language: Английский

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Alkynyl cyclopropanes in organic synthesis

Russian Chemical Bulletin, Journal Year: 2024, Volume and Issue: 73(1), P. 53 - 109

Published: Jan. 1, 2024

Language: Английский

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Enantioselective Multicomponent Electrochemical Difunctionalization of Terminal Alkynes

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 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.

Language: Английский

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Facile and General Electrochemical Diselenylation of Terminal Alkynes

ACS Sustainable Chemistry & Engineering, Journal Year: 2023, Volume and Issue: 11(6), P. 2607 - 2612

Published: Jan. 30, 2023

Difunctionalization of terminal alkynes is a cutting-edge method for producing trisubstituted alkenes. The methods employed, however, rely heavily on the use organometallic species with harsh conditions or transition metal-catalyzed multicomponent radical-mediated transformations. Herein, we report an electrochemical diselenylation to afford alkenes in antiselective fashion 100% atom economy. Moreover, this uses simple graphite as electrodes and MeCN solvent does not require high temperatures, which affords regioselectivity. success gram-scale reaction, great tolerance multiple functional groups, functionalization complex compounds all established value green technology.

Language: Английский

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