Cross-Coupling and Related Reactions: Connecting Past Success to the Development of New Reactions for the Future

Organometallics, Journal Year: 2018, Volume and Issue: 38(1), P. 3 - 35

Published: Nov. 27, 2018

Cross-coupling reactions, which were discovered almost 50 years ago, are widely used in both industry and academia. Even though cross-coupling reactions now represent mature technology, there is still a significant amount of research this area that aims to improve the scope these develop more efficient catalysts, make practical. In tutorial, brief background provided, then major advances over last 20 described. These include development improved ligands precatalysts for extension much wider range electrophiles. For example, common with sp3-hybridized electrophiles as well ester, amide, ether, aziridine substrates. many modern substrates, traditional palladium-based catalysts less than systems based on first-row transition metals such nickel. Conventional have also inspired related cross-electrophile decarboxylative couplings metallaphotoredox chemistry. The new probably at same stage 30 tutorial highlights how strategies may be applicable making

Language: Английский

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Asymmetric Ni-Catalyzed Radical Relayed Reductive Coupling

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(31), P. 13515 - 13522

Published: June 29, 2020

Alkene dicarbofunctionalizations enable the streamlined construction of aliphatic structures and have thus been subject intense research efforts. Despite significant progress, catalytic asymmetric variants remain scarce. Inspired by advantages reductive cross-coupling approaches, we present here a highly efficient intermolecular Ni-catalyzed dicarbofunctionalization alkenes. Two distinct readily available electrophiles, namely, Csp2- Csp3-halides, are added simultaneously across variety olefins (vinyl amides, vinyl boranes, phosphonates) at room temperature in regio- enantioselective manner. The reaction, devoid sensitive organometallic reagents, takes advantage an situ generated chiral alkyl Ni(III)-intermediate to ensure stereodefined outcome Csp3–Csp2 bond-forming reaction. An (l)-(+)-isoleucine bisoxazoline ligand presence coordinating sites on alkene key for successful these "asymmetric radical relayed couplings" (ARRRCs). Further, multiple transformations amides obtained this process showcase potential new methodology straightforward assembly building blocks such as primary secondary amines oxazolines, highlighting its synthetic utility.

Language: Английский

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Site-Selective Ni-Catalyzed Reductive Coupling of α-Haloboranes with Unactivated Olefins

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(40), P. 12765 - 12769

Published: Sept. 23, 2018

A mild, chemo- and site-selective catalytic protocol that allows for incorporating an alkylboron fragment into unactivated olefins is described. The use of internal enables C–C bond-formation at remote sp3 C–H sites, constituting a complementary conceptually different approach to existing borylation techniques are currently available centers.

Language: Английский

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Reactions of organoboron compounds enabled by catalyst-promoted metalate shifts

Chemical Society Reviews, Journal Year: 2019, Volume and Issue: 48(13), P. 3464 - 3474

Published: Jan. 1, 2019

This tutorial review describes recent developments in catalytic reaction design that involve catalyst-promoted 1,2-metalate shifts as a critical part of the mechanism.

Language: Английский

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Alkenyl Boronates: Synthesis and Applications

Chemistry - An Asian Journal, Journal Year: 2018, Volume and Issue: 14(3), P. 329 - 343

Published: Dec. 12, 2018

Abstract Organoboron compounds have become one of the most versatile building blocks in organic synthesis owing to their accessible and efficient conversion into many different functional groups. In particular, alkenyl boronates received a great deal attention as very reactive substrates Suzuki–Miyaura cross‐coupling reactions. Accordingly, efforts towards development methods prepare this type compound are ongoing. contribution, progress search for synthetic routes use variety transformations is accounted.

Language: Английский

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Carbopalladation of C–C σ-bonds enabled by strained boronate complexes

Nature Chemistry, Journal Year: 2018, Volume and Issue: 11(2), P. 117 - 122

Published: Nov. 27, 2018

Language: Английский

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Recent advances in asymmetric borylation by transition metal catalysis

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(23), P. 13129 - 13188

Published: Jan. 1, 2021

We provide a comprehensive overview of transition metal-catalysed asymmetric borylation processes to construct C–B, C–C, and other C–heteroatom bonds with considerable attention devoted the reaction modes mechanisms involved.

Language: Английский

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Iridium-Catalyzed Asymmetric Difunctionalization of C–C σ-Bonds Enabled by Ring-Strained Boronate Complexes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(30), P. 16508 - 16516

Published: July 20, 2023

Enantioenriched organoboron intermediates are important building blocks in organic synthesis and drug discovery. Recently, transition metal-catalyzed enantioselective 1,2-metalate rearrangements of alkenylboronates have emerged as an attractive protocol to access these valuable reagents by installing two different carbon fragments across C═C π-bonds. Herein, we report the development iridium-catalyzed asymmetric allylation-induced rearrangement bicyclo[1.1.0]butyl (BCB) boronate complexes enabled strain release, which allows difunctionalization C-C σ-bonds, including dicarbonation carboboration. This provides a variety enantioenriched three-dimensional 1,1,3-trisubstituted cyclobutane products bearing boronic ester that can be readily derivatized. Notably, reaction gives trans diastereoisomers result from anti-addition σ-bond, is contrast syn-additions observed for reactions promoted PdII-aryl other electrophiles our previous works. The diastereoselectivity has been rationalized based on combination experimental data density functional theory calculations, suggest BCB highly nucleophilic react via early states with low activation barriers.

Language: Английский

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Site‐Selective 1,2‐Dicarbofunctionalization of Vinyl Boronates through Dual Catalysis

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(11), P. 4370 - 4374

Published: Jan. 7, 2020

A modular, site-selective 1,2-dicarbofunctionalization of vinyl boronates with organic halides through dual catalysis is described. This reaction proceeds under mild conditions and characterized by excellent chemo- regioselectivity. It thus represents a complementary new technique for preparing densely functionalized alkyl boron architectures from simple accessible precursors.

Language: Английский

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Stereospecific 1,2‐Migrations of Boronate Complexes Induced by Electrophiles

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(39), P. 16859 - 16872

Published: June 27, 2020

The stereospecific 1,2-migration of boronate complexes is one the most representative reactions in boron chemistry. This process has been used extensively to develop powerful methods for asymmetric synthesis, with applications spanning from pharmaceuticals natural products. Typically, driven by displacement an α-leaving group, oxidation α-boryl radical, or electrophilic activation alkenyl complex. aim this article summarize recent advances rapidly expanding field electrophile-induced groups sp

Language: Английский

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