Catalytic asymmetric cationic shifts of aliphatic hydrocarbons

Nature, Год журнала: 2024, Номер 625(7994), С. 287 - 292

Опубликована: Янв. 10, 2024

Abstract Asymmetric catalysis is an advanced area of chemical synthesis, but the handling abundantly available, purely aliphatic hydrocarbons has proven to be challenging. Typically, heteroatoms or aromatic substructures are required in substrates and reagents facilitate efficient interaction with chiral catalyst. Confined acids have recently been introduced as tools for homogenous asymmetric catalysis, specifically enable processing small unbiased 1 . However, reactions which both substrate product not previously catalysed by such super strong confined acids. We describe here imidodiphosphorimidate-catalysed Wagner–Meerwein shift alkenyl cycloalkanes cycloalkenes excellent regio- enantioselectivity. Despite their long history high relevance synthesis biosynthesis, utilizing hydrocarbons, those originally reported Wagner Meerwein, had eluded catalysis.

Язык: Английский

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Applying statistical modeling strategies to sparse datasets in synthetic chemistry

Science Advances, Год журнала: 2025, Номер 11(1)

Опубликована: Янв. 1, 2025

The application of statistical modeling in organic chemistry is emerging as a standard practice for probing structure-activity relationships and predictive tool many optimization objectives. This review aimed tutorial those entering the area chemistry. We provide case studies to highlight considerations approaches that can be used successfully analyze datasets low data regimes, common situation encountered given experimental demands Statistical hinges on (what being modeled), descriptors (how are represented), algorithms modeled). Herein, we focus how various reaction outputs (e.g., yield, rate, selectivity, solubility, stability, turnover number) structures binned, heavily skewed, distributed) influence choice algorithm constructing chemically insightful models.

Язык: Английский

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Reinforced double-threaded slide-ring networks for accelerated hydrogel discovery and 3D printing

Chem, Год журнала: 2023, Номер 9(12), С. 3515 - 3531

Опубликована: Авг. 23, 2023

Язык: Английский

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Inverse design of chiral functional films by a robotic AI-guided system

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Окт. 4, 2023

Artificial chiral materials and nanostructures with strong tuneable chiroptical activities, including sign, magnitude, wavelength distribution, are useful owing to their potential applications in sensing, enantioselective catalysis, devices. Thus, the inverse design customized manufacturing of these is highly desirable. Here, we use an artificial intelligence (AI) guided robotic chemist accurately predict activities from experimental absorption spectra structure/process parameters, generate films targeted across full visible spectrum. The AI-chemist carries out entire process, film construction, characterization, testing. A machine learned reverse model using spectrum embedded descriptors developed optimal parameters for any property. series a dissymmetry factor as high 1.9 (gabs ~ 1.9) identified more than 100 million possible structures, feasible application circular polarization-selective color filters multiplex laser display switchable circularly polarized (CP) luminescence demonstrated. Our findings not only provide highest reported activity, but also have great fundamental value materials.

Язык: Английский

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Taming secondary benzylic cations in catalytic asymmetric S _N 1 reactions

Science, Год журнала: 2023, Номер 382(6668), С. 325 - 329

Опубликована: Окт. 19, 2023

Benzylic stereogenic centers are ubiquitous in natural products and pharmaceuticals. A potentially general, though challenging, approach toward their selective creation would be asymmetric unimolecular nucleophilic substitution (SN1) reactions that proceed through highly reactive benzylic cations. We now report a broadly applicable solution to this problem by identifying chiral counteranions pair with secondary cations engage catalytic C-C, C-O, C-N bond-forming excellent enantioselectivity. The critical cationic intermediate can accessed from different precursors via Lewis- or Brønsted acid catalysis. Key our strategy is the use of only weakly basic, confined posited prolong lifetime carbocation, thereby avoiding nonproductive deprotonation pathways corresponding styrene.

Язык: Английский

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Enantioselective functionalization of unactivated C(sp3)–H bonds through copper-catalyzed diyne cyclization by kinetic resolution

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Март 12, 2024

Site- and stereoselective C-H functionalization is highly challenging in the synthetic chemistry community. Although of vinyl cations has been vigorously studied C(sp

Язык: Английский

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Rh-Catalyzed Enantioselective Single-Carbon Insertion of Alkenes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(31), С. 21837 - 21846

Опубликована: Июль 26, 2024

The interest in the discovery and development of skeletal editing processes that selectively insert, exchange, or delete an atom organic molecules has significantly increased over last few years. However, this class proceed through creation a chiral center with high asymmetric induction have been largely unexplored. Herein, we report enantioselective single-carbon insertion aryl- alkyl-substituted alkenes mediated by catalytically generated Rh-carbynoid phosphate nucleophiles produce enantioenriched allylic phosphates (enantiomeric ratio (e.r.) = 89.5:10.5-99.5:0.5). key to process was diastereo- cyclopropanation alkene formation transient cyclopropyl-I

Язык: Английский

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Valence-isomer selective cycloaddition reaction of cycloheptatrienes-norcaradienes

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Март 14, 2024

Abstract The rapid and precise creation of complex molecules while controlling multiple selectivities is the principal objective in synthetic chemistry. Combining data science organic synthesis to achieve this goal an emerging trend, but few examples successful reaction designs are reported. We develop artificial neural network regression model using bond orbital predict chemical reactivities. Actual experimental verification confirms cycloheptatriene-selective [6 + 2]-cycloaddition utilizing nitroso compounds norcaradiene-selective [4 reactions employing benzynes. Additionally, a one-pot asymmetric achieved by telescoping enantioselective dearomatization non-activated benzenes cycloadditions. Computational studies provide rational explanation for seemingly anomalous occurrence thermally prohibited suprafacial without photoirradiation.

Язык: Английский

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Peroxycarbenium-Mediated Asymmetric Synthesis of 1,2-Dioxanes and 1,2-Dioxolanes

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(4), С. 3353 - 3359

Опубликована: Янв. 17, 2025

The endoperoxide scaffold is found in numerous natural products and synthetic substances of pharmaceutical interest. main challenge to their access remains the preparation chiral compounds due weakness peroxide bond, which limits scope available or applicable methods. Here, we demonstrate how peroxycarbenium species can be trapped by silylated nucleophiles with high enantioselectivities diastereoselectivities when applicable, using a imidophosphorimidate (IDPi) as catalyst. methodology broad, encompassing large variety enoxysilanes yielding 1,2-dioxanes 1,2-dioxolanes. Peroxides converted into alcohols trans-epoxides, was applied key step total synthesis ethyl plakortide Z, enhancing selectivity compared conventional Lewis acid-catalyzed transformation. Kinetic studies have shown that reaction necessitates an induction period, indicating formation silylium behaves true

Язык: Английский

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Asymmetric one-carbon ring expansion of diverse N-heterocycles via copper-catalyzed diyne cyclization

Science Advances, Год журнала: 2024, Номер 10(41)

Опубликована: Окт. 9, 2024

One-carbon ring expansion reaction of N-heterocycles has gained particular attention in the past decade because this method allows for conversion readily available into potentially useful complex ring-expanded N-heterocycles, which are inaccessible by traditional methods. However, catalytic asymmetric variant been rarely reported to date. Herein, we disclose an enantioselective one-carbon through chiral copper-catalyzed diyne cyclization, leading practical, atom-economic and divergent assembly array valuable bearing a quaternary stereocenter generally good excellent yields with enantioselectivities (up >99% ee). This protocol represents first example based on alkynes.

Язык: Английский

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