Reactions of organoboron compounds enabled by catalyst-promoted metalate shifts

Chemical Society Reviews, Год журнала: 2019, Номер 48(13), С. 3464 - 3474

Опубликована: Янв. 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.

Язык: Английский

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Alkenyl Boronates: Synthesis and Applications

Chemistry - An Asian Journal, Год журнала: 2018, Номер 14(3), С. 329 - 343

Опубликована: Дек. 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.

Язык: Английский

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Recent advances in asymmetric borylation by transition metal catalysis

Chemical Society Reviews, Год журнала: 2021, Номер 50(23), С. 13129 - 13188

Опубликована: Янв. 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.

Язык: 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, Год журнала: 2023, Номер 145(30), С. 16508 - 16516

Опубликована: Июль 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.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(11), С. 4370 - 4374

Опубликована: Янв. 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.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(39), С. 16859 - 16872

Опубликована: Июнь 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

Язык: Английский

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Rapid Access to Highly Functionalized Alkyl Boronates by NiH‐Catalyzed Remote Hydroarylation of Boron‐Containing Alkenes

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(39), С. 13860 - 13864

Опубликована: Июль 9, 2019

The direct and selective functionalization of relatively simple readily accessible precursors to produce highly functionalized alkyl boronates is a synthetically useful process. Herein we report NiH-catalyzed remote hydroarylation process that can, through synergistic combination chain walking subsequent cross-coupling, introduce an aryl group at the adjacent carbon atom under mild conditions. By means preliminary experiment with moderate enantioselectivity, it was shown asymmetric version could also be realized.

Язык: Английский

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Enantioselective Radical Addition/Cross‐Coupling of Organozinc Reagents, Alkyl Iodides, and Alkenyl Boron Reagents

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(40), С. 14245 - 14249

Опубликована: Авг. 7, 2019

Abstract A hybrid transition‐metal/radical process is described that results in the addition of organozinc reagents and alkyl halides across alkenyl boron an enantioselective catalytic fashion. The reaction can be accomplished both intermolecularly intramolecularly, providing useful product yields high enantioselectivities manifolds.

Язык: Английский

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Difunctionalization of C–C σ-Bonds Enabled by the Reaction of Bicyclo[1.1.0]butyl Boronate Complexes with Electrophiles: Reaction Development, Scope, and Stereochemical Origins

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(39), С. 16766 - 16775

Опубликована: Сен. 4, 2020

Difunctionalization reactions of C–C σ-bonds have the potential to streamline access molecules that would otherwise be difficult prepare. However, development such is challenging because are typically unreactive. Exploiting high ring-strain energy polycyclic carbocycles a common strategy weaken and facilitate reaction σ-bonds, but there limited examples highly strained being used in difunctionalization reactions. We demonstrate bicyclo[1.1.0]butyl boronate complexes (strain ca. 65 kcal/mol), which were prepared by reacting boronic esters with lithium, react electrophiles achieve diastereoselective central σ-bond unit. The shows broad substrate scope, range different successfully employed form diverse set 1,1,3-trisubstituted cyclobutanes (>50 examples) diastereoselectivity. diastereoselectivity observed has been rationalized based on combination experimental data DFT calculations, suggests separate concerted stepwise mechanisms operating, depending upon migrating substituent electrophile used.

Язык: Английский

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Copper-Catalyzed Enantioconvergent Radical Suzuki–Miyaura C(sp³)–C(sp²) Cross-Coupling

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(46), С. 19652 - 19659

Опубликована: Ноя. 4, 2020

A copper-catalyzed enantioconvergent Suzuki–Miyaura C(sp3)–C(sp2) cross-coupling of various racemic alkyl halides with organoboronate esters has been established in high enantioselectivity. Critical to the success is use a chiral cinchona alkaloid-derived N,N,P-ligand for not only enhancing reducing capability copper catalyst favor stereoablative radical pathway over stereospecific SN2-type process but also providing an ideal environment achieve challenging enantiocontrol highly reactive species. The reaction broad scope respect both coupling partners, covering aryl- and heteroarylboronate esters, as well benzyl-, heterobenzyl-, propargyl bromides chlorides good functional group compatibility. Thus, it provides expedient access toward range useful enantioenriched skeletons featuring tertiary benzylic stereocenters.

Язык: Английский

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