Angewandte Chemie, Год журнала: 2019, Номер 131(40), С. 14383 - 14387
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
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
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
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
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
140
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
128
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
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
Процитировано
90
Journal of the American Chemical Society, Год журнала: 2018, Номер 140(46), С. 15621 - 15625
Опубликована: Ноя. 9, 2018
A catalytic, enantioselective method for the preparation of chiral, non-racemic, alkylboronic esters bearing two vicinal stereogenic centers is described. The reaction proceeds via a 1,2-migration zwitterionic thiiranium–boronate complex to give exclusively anti carbosulfenylation products. broad scope aryl groups migrate with good yield and excellent enantioselectivity (up 99:1 e.r.). Similarly, range di- trisubstituted alkenylboronic are competent partners. This provides access both secondary tertiary chiral esters.
Язык: Английский
Процитировано
88
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
Advanced Synthesis & Catalysis, Год журнала: 2019, Номер 362(11), С. 2077 - 2087
Опубликована: Дек. 24, 2019
Abstract 1,2‐Boron ate rearrangements represent a fundamental class of transformations to establish new C−C bonds while retaining the valuable boron moiety in product. In established ionic processes, complex is activated by an external electrophile induce 1,2‐migration from adjacent sp 3 or 2 carbon atom. Recently, two complementary radical polar crossover approaches have been explored for both classes, 1,2‐migrations and centers. This review describes general concepts this emerging research field summarizes recent developments radical‐induced carbon. magnified image
Язык: Английский
Процитировано
79