Palladium-Catalyzed Enantioselective Multicomponent Cross-Coupling of Trisubstituted Olefins DOI

Wenyi Huang,

Yang Xi, Deng Pan

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(24), С. 16892 - 16901

Опубликована: Июнь 6, 2024

The development of a catalytic method for stereogenic carbon center formation holds immense significance in organic synthesis. Transition-metal-catalyzed cross-coupling reaction has been regarded as straightforward and efficient tool stereoselectively forging C–C bond. Nevertheless, the creation acyclic all-carbon quaternary-containing vicinal stereocenters remains notoriously challenging within domain chemistry despite their prominence various bioactive small molecules. Herein, we describe palladium-catalyzed asymmetric multicomponent trisubstituted alkene with aryl diazonium salts arylboronic acids to realize tertiary-quaternary centers high regio-, distereo-, enantioselectivity. Specifically, precise manipulation stereoconfiguration alkenes enables divergent stereoselective reaction, thus allowing facile construction all four enantiomers. Harnessing ligand-swap strategy involving chiral bisoxazoline an achiral fumarate individually accelerates enantioselective migratory insertion reductive elimination step process, supported by density functional theory (DFT) calculations, obviating requirement neighboring directing group internal olefin skeleton.

Язык: Английский

Reactions of organoboron compounds enabled by catalyst-promoted metalate shifts DOI

Sheila Namirembe,

James P. Morken

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

Процитировано

215
Alkenyl Boronates: Synthesis and Applications DOI
Javier Carreras, Ana Caballero, Pedro J. Pérez

и другие.

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

Процитировано

202
Recent advances in asymmetric borylation by transition metal catalysis DOI
Jiefeng Hu, Matthias Ferger, Zhuangzhi Shi

и другие.

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

Процитировано

179
Iridium-Catalyzed Asymmetric Difunctionalization of C–C σ-Bonds Enabled by Ring-Strained Boronate Complexes DOI Creative Commons

Hong‐Cheng Shen,

Mihai V. Popescu, Ze‐Shu Wang

и другие.

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

Процитировано

47
Site‐Selective 1,2‐Dicarbofunctionalization of Vinyl Boronates through Dual Catalysis DOI
Shang‐Zheng Sun, Yaya Duan, Riccardo S. Mega

и другие.

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

Процитировано

139
Stereospecific 1,2‐Migrations of Boronate Complexes Induced by Electrophiles DOI Creative Commons
Hui Wang, Changcheng Jing, Adam Noble

и другие.

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

Процитировано

127
Rapid Access to Highly Functionalized Alkyl Boronates by NiH‐Catalyzed Remote Hydroarylation of Boron‐Containing Alkenes DOI
Yao Zhang, Bo Han, Shaolin Zhu

и другие.

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

Процитировано

116
Enantioselective Radical Addition/Cross‐Coupling of Organozinc Reagents, Alkyl Iodides, and Alkenyl Boron Reagents DOI
Matteo Chierchia, Peilin Xu, Gabriel J. Lovinger

и другие.

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

Процитировано

116
Copper-Catalyzed Enantioconvergent Radical Suzuki–Miyaura C(sp3)–C(sp2) Cross-Coupling DOI
Shengpeng Jiang, Xiaoyang Dong, Qiang‐Shuai Gu

и другие.

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

Процитировано

90
An Olefinic 1,2‐Boryl‐Migration Enabled by Radical Addition: Construction ofgem‐Bis(boryl)alkanes DOI
Binlin Zhao, Zexian Li, Yixiao Wu

и другие.

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(28), С. 9448 - 9452

Опубликована: Май 6, 2019

A series of in situ formed alkenyl diboronate complexes from Grignard reagents (commercially available or prepared bromides and Mg) with B2 Pin2 (bis(pinacolato)diboron) react diverse alkyl halides by a Ru photocatalyst to give various gem-bis(boryl)alkanes. Alkyl radicals add efficiently the complexes, adduct radical anions undergo radical-polar crossover, specifically, 1,2-boryl-anion shift boron α-carbon sp2 center. This transformation shows good functional-group compatibility can serve as powerful synthetic tool for late-stage functionalization complex compounds. Measurements quantum yield reveal that radical-chain mechanism is operative which diboronates acts reductive quencher excited state photocatalyst.

Язык: Английский

Процитировано

88