Orthogonal Regulation of Nucleophilic and Electrophilic Sites in Pd‐Catalyzed Regiodivergent Couplings between Indazoles and Isoprene

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(15), P. 8321 - 8328

Published: Jan. 19, 2021

Abstract Depending on the reactant property and reaction mechanism, one major regioisomer can be favored in a that involves multiple active sites. Herein, an orthogonal regulation of nucleophilic electrophilic sites regiodivergent hydroamination isoprene with indazoles is demonstrated. Under Pd‐hydride catalysis, 1,2‐ or 4,3‐insertion pathway respect to could controlled by choice ligands. In terms indazoles, occurs at either N 1 ‐ 2 ‐position governed acid co‐catalysts. Preliminary experimental studies have been performed rationalize mechanism regioselectivity. This study not only contributes practical tool for selective functionalization isoprene, but also provides guide manipulate regioselectivity ‐functionalization indazoles.

Language: Английский

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Modern Synthetic Methods for the Stereoselective Construction of 1,3-Dienes

Molecules, Journal Year: 2021, Volume and Issue: 26(2), P. 249 - 249

Published: Jan. 6, 2021

The 1,3-butadiene motif is widely found in many natural products and drug candidates with relevant biological activities. Moreover, dienes are important targets for synthetic chemists, due to their ability give access a wide range of functional group transformations, including broad C-C bond-forming processes. Therefore, the stereoselective preparation have attracted much attention over past decades, search new protocols continues unabated. aim this review an overview diverse methodologies that emerged last decade, focus on processes meet requirements efficiency sustainability modern organic chemistry.

Language: Английский

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Hydroelementation of diynes

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(3), P. 869 - 994

Published: Jan. 1, 2022

This review highlights the hydroelementation reactions of conjugated and separated diynes, which depending on process conditions, catalytic system, as well type reagents, leads to formation various products: enynes, dienes, allenes, polymers, or cyclic compounds. The presence two triple bonds in diyne structure makes these compounds important reagents but selective product is often difficult owing problems associated with maintaining appropriate reaction regio- stereoselectivity. Herein we this topic gain knowledge reactivity diynes systematise range information relating their use reactions. divided according addition E-H (E = Mg, B, Al, Si, Ge, Sn, N, P, O, S, Se, Te) bond bond(s) diyne, reagent used, formed. Not only are comprehensively discussed, synthetic potential obtained products also presented. majority published research included within review, illustrating limitations processes, intent showcase power transformations synthesis materials chemistry.

Language: Английский

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Ni-Catalyzed Enantioselective Hydrofunctionalizations of 1,3-Dienes

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(24), P. 15638 - 15647

Published: Dec. 6, 2022

Ni-catalyzed enantioselective hydrofunctionalizations of conjugated dienes are particularly demanding reactions to devise because they require not only addressing the inherent challenges associated with development an transformation but also overcoming all other aspects selective catalysis (chemoselectivity, regioselectivity, diastereoselectivity, etc.). However, value-added nature chiral allylic and homoallylic derivatives obtained by these methods, lack efficient alternatives, use earth-abundant first-row transition metal have led renewed interest over past decade. In this Perspective, we give overview developments in field, from original findings (often dating back last century) most recent contributions. Emphasis is placed on hydrofunctionalization agent (C(sp), C(sp2), C(sp3), N, P, or O).

Language: Английский

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Photoinduced Cobalt Catalysis for the Reductive Coupling of Pyridines and Dienes Enabled by Paired Single‐Electron Transfer**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 7, 2023

Abstract Selective hydroarylation of dienes has potential to provide swift access useful building blocks. However, most existing methods rely on stabilised by an aromatic group and transmetallation or nucleophilic attack steps require electron‐rich aryl coupling partners. As such, there are few examples which tolerate wide‐spread heteroarenes such as pyridine. Whilst allylic C−H functionalisation could be considered alternative approach, the positional selectivity unsymmetrical substrates is hard control. Here, we report a general approach for selective hydropyridylation under mild conditions using metal catalysed hydrogen‐atom transfer. Photoinduced, reductive enable simultaneous formation cobalt‐hydride catalyst persistent radical easily‐synthesised pyridyl phosphonium salts. This facilitates in traceless manner at C4‐position wide‐range pyridine substrates. The mildness method underscored its functional‐group tolerance demonstrated applications late‐stage functionalisation. Based combination experimental computational studies, propose mechanistic pathway proceeds through non‐reversible transfer (HAT) from cobalt hydride species uniquely presence other olefins due much higher relative barrier associated with olefin HAT.

Language: Английский

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Photoinduced Copper‐Catalyzed Asymmetric Three‐Component Radical 1,2‐Azidooxygenation of 1,3‐Dienes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 24, 2024

Abstract Radical‐involved multicomponent difunctionalization of 1,3‐dienes has recently emerged as a promising strategy for rapid synthesis valuable allylic compounds in one‐pot operation. However, the expansion radical scope and enantiocontrol remain two major challenges. Herein, we describe an unprecedented photoinduced copper‐catalyzed highly enantioselective three‐component 1,2‐azidooxygenation with readily available azidobenziodazolone reagent carboxylic acids. This mild protocol exhibits broad substrate scope, high functional group tolerance, exceptional control over chemo‐, regio‐ enantioselectivity, providing practical access to diverse azidated chiral esters. Mechanistic studies imply that copper complex is implicated bifunctional catalyst both photoredox catalyzed azidyl generation C−O cross‐coupling.

Language: Английский

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Copper-Catalyzed 1,2-Sulfonyletherification of 1,3-Dienes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 2939 - 2944

Published: April 11, 2024

A selective three-component 1,2-sulfonyl etherification of aryl 1,3-dienes enabled by copper catalysis to afford biologically interesting alkenyl 1,2-sulfone ether derivatives through C–S and C–O bond formation is described. The protocol proceeds with the sulfonyl chloride alcohols under simple, mild, base-free conditions, providing a straightforward route sulfonylated allyl compounds broad functional group tolerance excellent chemo- regioselectivity. Mechanistic studies indicate that alkene difunctionalization includes key copper-mediated single-electron transfer process.

Language: Английский

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Stereoselective synthesis of substituted 1,3-dienes from propargylic esters: electrophilic-metal or redox catalysis?

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(5), P. 1384 - 1396

Published: March 22, 2024

Language: Английский

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Transition metal catalyzed asymmetric multicomponent reactions of unsaturated compounds using organoboron reagents

Chemical Communications, Journal Year: 2020, Volume and Issue: 57(4), P. 441 - 459

Published: Dec. 10, 2020

Transition metal-catalyzed asymmetric multicomponent reactions using organoboron compounds have been utilized extensively for C–B, C–C, and other bond-forming reactions. This feature article highlights the important discoveries in this topic.

Language: Английский

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Copper‐Catalyzed Borylative Couplings with C−N Electrophiles

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(46), P. 20278 - 20289

Published: June 16, 2020

Copper-catalyzed borylative multicomponent reactions (MCRs) involving olefins and C-N electrophiles are a powerful tool to rapidly build up molecular complexity. The products from these contain multiple functionalities, such as amino, cyano boronate groups, that ubiquitous in medicinal process chemistry programs. MCRs particularly attractive because they use relatively abundant non-toxic catalyst selectively deliver high-value simple feedstocks olefins. In this Minireview, we explore emerging field survey the union of allenes, dienes, styrenes other olefins, with imines, nitriles related electrophiles.

Language: Английский

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