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

Wenyi Huang,

Yang Xi,

Deng Pan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16892 - 16901

Published: June 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.

Language: Английский

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

Sheila Namirembe,

James P. Morken

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

Citations

213
Alkenyl Boronates: Synthesis and Applications DOI
Javier Carreras, Ana Caballero, Pedro J. Pérez

et al.

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

Citations

197
Recent advances in asymmetric borylation by transition metal catalysis DOI
Jiefeng Hu, Matthias Ferger, Zhuangzhi Shi

et al.

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

Citations

175
Site‐Selective 1,2‐Dicarbofunctionalization of Vinyl Boronates through Dual Catalysis DOI
Shang‐Zheng Sun, Yaya Duan, Riccardo S. Mega

et al.

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

Citations

139
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

et al.

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

Citations

45
Stereospecific 1,2‐Migrations of Boronate Complexes Induced by Electrophiles DOI Creative Commons
Hui Wang, Changcheng Jing, Adam Noble

et al.

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

Citations

123
Enantioselective Radical Addition/Cross‐Coupling of Organozinc Reagents, Alkyl Iodides, and Alkenyl Boron Reagents DOI
Matteo Chierchia, Peilin Xu, Gabriel J. Lovinger

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(40), P. 14245 - 14249

Published: Aug. 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.

Language: Английский

Citations

115
Rapid Access to Highly Functionalized Alkyl Boronates by NiH‐Catalyzed Remote Hydroarylation of Boron‐Containing Alkenes DOI
Yao Zhang, Bo Han, Shaolin Zhu

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(39), P. 13860 - 13864

Published: July 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.

Language: Английский

Citations

114
Copper-Catalyzed Enantioconvergent Radical Suzuki–Miyaura C(sp3)–C(sp2) Cross-Coupling DOI
Shengpeng Jiang, Xiaoyang Dong, Qiang‐Shuai Gu

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(46), P. 19652 - 19659

Published: Nov. 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.

Language: Английский

Citations

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

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(28), P. 9448 - 9452

Published: May 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.

Language: Английский

Citations

88