Catalytic Enantioselective Boryl and Silyl Substitution with Trifluoromethyl Alkenes: Scope, Utility, and Mechanistic Nuances of Cu–F β-Elimination DOI
Paulo H. S. Paioti, Juan del Pozo,

Malte S. Mikus

и другие.

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(50), С. 19917 - 19934

Опубликована: Дек. 6, 2019

Catalytic enantioselective methods are introduced that allow access to a variety of allyl boronates and silanes contain difluoroalkene unit; the resulting products may be used for preparation organofluorine compounds in high enantiomeric purity. Furthermore, number key mechanistic aspects transformations have been investigated analyzed. Thus, first, an NHC–Cu-catalyzed method boryl substitution with F3C-substituted alkenes is introduced. These processes, unlike previously reported strategies, applicable alkyl as well aryl substituted substrates, afford bearing moiety (up 98% yield 95:5 er). Second, corresponding silyl substitutions, first cases their kind, presented 94% 97:3 Third, experimental computational (DFT) investigations described shed light on catalytic processes. Evidence (X-ray structures Cu–alkyl intermediates kinetic studies) put forth illustrating initial Cu–boryl Cu–silyl addition significantly faster than ensuing Cu–F elimination, latter step can facilitated by either mild Lewis acid (e.g., Li or Na cation) nucleophilic promoter alkoxide). findings together DFT studies demonstrate β-elimination probably proceeds anti-stereochemistry. Representative ways through which new understanding rationalize disclosed findings, improve transformation, develop diastereo- provided. For example, explanation provided regarding why bisphosphine–Cu complexes do not efficiently promote substitutions aryl-substituted but facile, how size ligand impact regioselectivity efficiency.

Язык: Английский

Recent Developments in Organoboron Chemistry: Old Dogs, New Tricks DOI Creative Commons

James W. B. Fyfe,

Allan J. B. Watson

Chem, Год журнала: 2017, Номер 3(1), С. 31 - 55

Опубликована: Июль 1, 2017

Язык: Английский

Процитировано

532
Synergistic Dual Transition Metal Catalysis DOI

U. Bin Kim,

Da Jung Jung,

Hyun Ji Jeon

и другие.

Chemical Reviews, Год журнала: 2020, Номер 120(24), С. 13382 - 13433

Опубликована: Ноя. 29, 2020

Synergistic catalysis, a type of plural catalysis which utilizes at least two different catalysts to enable reaction between separately activated substrates, has unlocked plethora previously unattainable transformations and novel chemical reactivity. Despite the appreciable utility synergistic specific examples involving transition metals have been limited, as ensuring judicious choice parameters prevent deactivation catalysts, undesirable monocatalytic event(s) leading side products, or premature termination other potentially troublesome outcomes present formidable challenge. Excluding those driven by photocatalytic mechanisms, this review will highlight reported reactions that make use simultaneous catalytic cycles metal catalysts.

Язык: Английский

Процитировано

298
Copper-boryl mediated organic synthesis DOI Creative Commons

David Hemming,

Russell G. Fritzemeier,

Stephen A. Westcott

и другие.

Chemical Society Reviews, Год журнала: 2018, Номер 47(19), С. 7477 - 7494

Опубликована: Янв. 1, 2018

The diverse applications of copper-catalyzed borylation, which has become an essential strategy in modern synthetic organic chemistry, are reviewed and illustrated.

Язык: Английский

Процитировано

288
Asymmetric Synthesis of Secondary and Tertiary Boronic Esters DOI
Beatrice S. L. Collins,

Claire M. Wilson,

Eddie L. Myers

и другие.

Angewandte Chemie International Edition, Год журнала: 2017, Номер 56(39), С. 11700 - 11733

Опубликована: Май 18, 2017

Abstract Non‐racemic chiral boronic esters are recognised as immensely valuable building blocks in modern organic synthesis. Their stereospecific transformation into a variety of functional groups—from amines and halides to arenes alkynes—along with their air moisture stability, has established them an important target for asymmetric Efforts towards the stereoselective synthesis secondary tertiary alkyl have spanned over five decades underpinned by wealth reactivity platforms, drawing on unique varied boron. This Review summarizes strategies esters, from seminal hydroboration methods H. C. Brown current state art.

Язык: Английский

Процитировано

276
Nickel-Catalyzed Asymmetric Reductive Cross-Coupling To Access 1,1-Diarylalkanes DOI
Kelsey E. Poremba, Nathaniel T. Kadunce,

Naoyuki Suzuki

и другие.

Journal of the American Chemical Society, Год журнала: 2017, Номер 139(16), С. 5684 - 5687

Опубликована: Апрель 13, 2017

An asymmetric Ni-catalyzed reductive cross-coupling of (hetero)aryl iodides and benzylic chlorides has been developed to prepare enantioenriched 1,1-diarylalkanes. As part these studies, a new chiral bioxazoline ligand, 4-heptyl-BiOX (L1), was in order obtain products synthetically useful yield enantioselectivity. The reaction tolerates variety heterocyclic coupling partners, including pyridines, pyrimidines, indoles, piperidines.

Язык: Английский

Процитировано

260
Nickel‐Catalyzed Asymmetric Reductive Diarylation of Vinylarenes DOI

David R. Anthony,

Qiao Lin,

Judith Baudet

и другие.

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(10), С. 3198 - 3202

Опубликована: Янв. 25, 2019

Abstract A nickel‐catalyzed asymmetric diarylation reaction of vinylarenes enables the preparation chiral α,α,β‐triarylated ethane scaffolds, which exist in a number biologically active molecules. The use reducing conditions with aryl bromides as coupling partners obviates need for stoichiometric organometallic reagents and tolerates broad range functional groups. application an N ‐oxyl radical ligand to nickel catalyst represents novel approach facilitate cross‐coupling reactions.

Язык: Английский

Процитировано

252
Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes DOI
Ji‐Shu Zhang, Long Liu, Tieqiao Chen

и другие.

Chemistry - An Asian Journal, Год журнала: 2018, Номер 13(17), С. 2277 - 2291

Опубликована: Июнь 13, 2018

Abstract Three‐component reactions can directly convert three reactants into the desired products in one pot and thus greatly shorten synthetic path. Recently, transition‐metal catalysis has been applied difunctionalization of alkenes remarkable progress achieved to facilitate construction a wide range functional molecules with high atom‐ step‐economic efficiency. This Focus Review highlights recent advances this field.

Язык: Английский

Процитировано

251
Copper-Catalyzed Borylative Difunctionalization of π-Systems DOI
Andrew Whyte, Alexa Torelli, Bijan Mirabi

и другие.

ACS Catalysis, Год журнала: 2020, Номер 10(19), С. 11578 - 11622

Опубликована: Авг. 25, 2020

Organoboronates represent a cornerstone functional group in modern synthesis owing to their unique reactivity and divergent synthetic capability. Copper catalysis has become one of the most powerful methods stereoselectively install boron across diverse π-systems. Additionally, this method affords tremendous versatility enabled by difunctionalization π-system addition an electrophile. This review covers known electrophiles intercept catalytic intermediates borylative strategies that have been reported up end May 2020.

Язык: Английский

Процитировано

209
Catalyst Controlled Regiodivergent Arylboration of Dienes DOI
Stephen R. Sardini, M. Kevin Brown

Journal of the American Chemical Society, Год журнала: 2017, Номер 139(29), С. 9823 - 9826

Опубликована: Июль 12, 2017

A method for the regiodivergent arylboration of dienes is presented. These reactions allow formation a diverse range synthetically versatile products from simple precursors. Through mechanistic studies, these likely operate by initial addition Cu–Bpin complex across diene followed Pd-catalyzed cross coupling with an aryl halide or pseudohalide.

Язык: Английский

Процитировано

193
Enantioselective benzylic C–H arylation via photoredox and nickel dual catalysis DOI Creative Commons
Xiaokai Cheng,

Huangzhe Lu,

Zhan Lu

и другие.

Nature Communications, Год журнала: 2019, Номер 10(1)

Опубликована: Авг. 7, 2019

Abstract The asymmetric cross-coupling reaction is developed as a straightforward strategy toward 1,1-diaryl alkanes, which are key skeleton in series of natural products and bioactive molecules recent years. Here we report an enantioselective benzylic C(sp 3 )−H bond arylation via photoredox/nickel dual catalysis. Sterically hindered chiral biimidazoline ligands designed for this reaction. Readily available alkyl benzenes aryl bromides with various functional groups tolerance can be easily directly transferred to useful alkanes including pharmaceutical intermediates molecules. This proceeds smoothly under mild conditions without the use external redox reagents.

Язык: Английский

Процитировано

187