Rhodium‐Catalyzed Dynamic Kinetic Asymmetric Hydrosilylation to Access Silicon‐Stereogenic Center

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(51)

Опубликована: Ноя. 4, 2022

Abstract Strategies on the construction of enantiomerically pure silicon‐stereogenic silanes generally relies desymmetrization prochiral and symmetric substrates. However, dynamic kinetic asymmetric transformations organosilicon compounds have remained underdeveloped unforeseen owing to a lack an effective method for deracemization static silicon stereocenters. Here we report first Rh‐catalyzed intramolecular hydrosilylation (DyKAH) with “silicon‐centered” racemic hydrosilanes that enables facile preparation benzosiloles in good yields excellent enantioselectivities. The special rhodium catalyst controlled by non‐diastereopure‐type mixed phosphine‐phosphoramidite ligand axial chirality multiple stereocenters can induce enantioselectivity efficiently this novel DyKAH reaction. Density functional theory (DFT) calculations suggest amide moiety chiral plays important role facilitating S N 2 substitution chloride ion realize inversion center.

Язык: Английский

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Catalytic asymmetric silicon-carbon bond-forming transformations based on Si-H functionalization

Science China Chemistry, Год журнала: 2023, Номер 66(6), С. 1654 - 1687

Опубликована: Май 4, 2023

Язык: Английский

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A Fusion of Molecular Imprinting Technology and Siloxane Chemistry: A Way to Advanced Hybrid Nanomaterials

Nanomaterials, Год журнала: 2023, Номер 13(2), С. 248 - 248

Опубликована: Янв. 6, 2023

Molecular imprinting technology is a well-known strategy to synthesize materials with predetermined specificity. For fifty years, the “classical” approach assumed creation of “memory sites” in organic polymer matrix by template molecule that interacts functional monomer prior polymerization and removal. However, phenomenon material’s “memory” provided “footprint” chemical entity was first observed on silica-based nearly century ago. Through molecular has attracted attention many scientists. Different forms molecularly imprinted materials, even nanoscale, were elaborated, predominantly using polymers induce “memory”. This field expanded quickly recent providing versatile tools for separation or detection numerous compounds macromolecules. In this review, we would like emphasize role process formation highly specific siloxane-based nanomaterials. The distinct chemistry siloxanes provides an opportunity facile functionalization surfaces nanomaterials, enabling us introduce additional properties way vast applications such as detectors separators. It also allows catalyzing reactions microreactors facilitate synthesis. Finally, it determines biocompatibility, which opens drug delivery nanomedicine. Thus, brief outlook discussion current state art nanomaterials will be provided. Those aspects presented context practical various areas medicine. future perspectives pointed out.

Язык: Английский

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Single-Walled Cluster Nanotubes for Single-Atom Catalysts with Precise Structures

Journal of the American Chemical Society, Год журнала: 2023, Номер 146(1), С. 450 - 459

Опубликована: Дек. 27, 2023

Spatially confining isolated atomic sites in low-dimensional nanostructures is a promising strategy for preparing high-performance single-atom catalysts (SACs). Herein, fascinating polyoxometalate cluster-based single-walled nanotubes (POM-SWNTs) with atomically precise structures, uniform diameter, and single-cluster wall thickness are constructed by lacunary POM clusters (PW11 P2W17 clusters). Isolated metal centers accurately incorporated into the PW11-SWNTs P2W17-SWNTs supports. The structures of resulting MPW11-SWNTs MP2W17-SWNTs well established (M = Cu, Pt). Molecular dynamics simulations demonstrate stability POM-SWNTs. Furthermore, turnover frequency PtP2W17-SWNTs 20 times higher than that PtP2W17 cluster units 140 Pt nanoparticles alcoholysis dimethylphenylsilane. Theoretical studies indicate incorporating atom support induces straightforward electron transfer between them, combining nanoconfined environment to enhance catalytic activity PtP2W17-SWNTs. This work shows feasibility using subnanometric assemble nanotubes, highlighting their potential prepare superior SACs structures.

Язык: Английский

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Overcoming synthetic challenges in developing High-Performance polybenzoxazine from Diamine-Functionalized Double-Decker silsesquioxane (DDSQ) cage

European Polymer Journal, Год журнала: 2025, Номер unknown, С. 113929 - 113929

Опубликована: Апрель 1, 2025

Язык: Английский

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Synthesis of Alkynylsilanes: A Review of the State of the Art

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(11), С. 2382 - 2431

Опубликована: Апрель 12, 2024

Abstract This contribution offers a comprehensive overview of methods for forging sp C−Si bonds. Over time, alkynylsilanes (silylacetylenes), once considered mere byproducts hydrosilylation processes, have become essential building blocks in organic synthesis. literature review traces the evolution their synthesis, from traditional methodologies relying on organolithium and organomagnesium compounds to more advanced cross‐coupling reactions involving hydro‐ carbosilanes. Focused primarily past 25 years (2000–2024), it also extensively references significant historical breakthroughs. By analyzing synthetic methodologies, not only survey current state knowledge but identifies areas improvement. Furthermore, emphasize importance 1‐alkynylsilanes (1‐silyl‐1‐alkynes), selected applications these are highlighted, confirming potential

Язык: Английский

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Cobalt-catalyzed dehydrogenative cross-coupling reaction: Selective access to dihydrosiloxanes, hydrosiloxanes and functionalized silsesquioxanes

Journal of Catalysis, Год журнала: 2023, Номер 423, С. 1 - 9

Опубликована: Апрель 27, 2023

Disclosed is a mild, scalable, and chemoselective cross-dehydrogenative functionalization protocol for the construction of Si−O−Si moieties under cobalt catalysis. The reaction has broad scope can be used to synthesize wide range silicon building blocks, including challenging dihydrosiloxanes functionalized silsesquioxanes. Most importantly, results are placed into context by benchmarking with state-of-the-art methods. Remarkably, utilized PNP-Co catalyst enables development further synthetic strategies such as one-pot sequential silanolysis/alcoholysis process or unprecedented dehydrocoupling between germanol hydrosilane.

Язык: Английский

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Photocatalytic dehydrogenative coupling of silanes with alcohols triggered by light-induced sulfur vacancies on CdS nanosheets

Journal of Catalysis, Год журнала: 2023, Номер 428, С. 115154 - 115154

Опубликована: Окт. 1, 2023

Язык: Английский

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An unusual autocatalysis with an air-stable Pd complex to promote enantioselective synthesis of Si-stereogenic enynes

Chemical Science, Год журнала: 2022, Номер 14(5), С. 1123 - 1131

Опубликована: Дек. 21, 2022

A highly enantioselective palladium-catalyzed hydrosilylation of 1,3-diynes with dihydrosilanes was established for the facile preparation Si-stereogenic enynes and an enyne-linked chiral polymer (polyenyne) in good yields excellent ees.

Язык: Английский

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Electrifying synthesis of organosilicon compounds – from electrosynthesis to electrocatalysis

Inorganic Chemistry Frontiers, Год журнала: 2023, Номер 10(5), С. 1382 - 1394

Опубликована: Янв. 1, 2023

Organosilicon compounds via electrosynthesis – the recent developments and further challenges.

Язык: Английский

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