Geminal bis(silanes) are versatile synthetic building blocks owing to their stability and propensity to undergo a variety of transformations. However, the scarcity of catalytic methods for their synthesis limits their structural diversity and thus their utility for further applications. Herein we report a new method for synthesis of geminal bis(silanes) by means of iron-catalyzed dihydrosilylation of alkynes. Iron catalysts were distinctly superior to the other tested catalysts, which clearly demonstrates that novel reactivity can be found by using iron catalysts. This method features 100% atom economy, regiospecificity, mild reaction conditions, and readily available starting materials. Using this method, we prepared a new type of geminal bis(silane) with secondary silane moieties, the Si–H bonds of which can easily undergo various transformations, facilitating the synthetic applications of these compounds. Preliminary mechanistic studies demonstrated that the reaction proceeds via two iron-catalyzed hyd...

Iron-Catalyzed Dihydrosilylation of Alkynes: Efficient Access to Geminal Bis(silanes)

Cobalt-Catalyzed Asymmetric Synthesis of gem-Bis(silyl)alkanes by Double Hydrosilylation of Aliphatic Terminal Alkynes

A crystalline two-coordinate cyclic (alkyl)(amino)silylene (1) was successfully synthesized and isolated. Its 29Si NMR and UV/Vis spectra indicate that the electronic properties of 1 fall between those of cyclic dialkylsilylenes and diaminosilylenes. At very low temperature, the color of a solution of 1 turned from colorless to yellow, which was monitored by UV/Vis spectroscopy. DFT calculations supported the hypothesis that head-to-head dimers (disilenes) with a very long Si–Si distance are formed at such low temperatures. Although 1 is thermally stable, it readily undergoes cycloadditions, Si−H insertions, and photochemical reactions with benzene similar to dialkylsilylenes. At higher temperatures, 1 is also susceptible to intermolecular benzylic C−H insertion reactions, as well as unprecedented dehydrogenation reactions with cyclohexa-1,4-diene and 9,10-dihydroanthracene to afford benzene and anthracene, respectively.

A Two-Coordinate Cyclic (Alkyl)(amino)silylene: Balancing Thermal Stability and Reactivity

We describe the design and development of the first catalytic asymmetric vinylogous Prins cyclization This reaction constitutes an efficient approach for highly diastereo- and enantioselective synthesis of tetrahydrofurans (THFs) and is catalyzed by a confined chiral imidodiphosphoric acid (IDP) Aromatic and heteroaromatic aldehydes react with various 3,5-dien-1-ols to afford 2,3-disubstituted THFs in excellent selectivity (dr > 20:1, er up to 99:1) Aliphatic aldehydes react with similarly excellent results when a highly acidic imidodiphosphorimidate (IDPi) catalyst is used With a racemic dienyl alcohol, the reaction proceeds via a kinetic resolution DFT calculations suggest an explanation for unusually high stereoselectivity

Catalytic Asymmetric Vinylogous Prins Cyclization: A Highly Diastereo- and Enantioselective Entry to Tetrahydrofurans

The unique steric effect of geminal bis(silane) [(R3Si)2CH] allows an exo-selective intermolecular Diels–Alder reaction of geminal bis(silyl) dienes with α,β-unsaturated carbonyl compounds. The approach shows good generality to form ortho–trans cyclohexenes in good yields with high exo-selectivity and high enantioselectivity in some asymmetric cases. The excellent exo-stereocontrol aptitude of (R3Si)2CH group is highlighted by comparing with R3SiCH2 and R3Si groups, which leads to endo-selectivity predominantly. The conformational analysis of dienes suggests that (R3Si)2CH group effectively shields both sides of the diene moiety, ensuring the desired exo-selectivity. Moreover, the geminal bis(silane) can be further functionalized to transform the resulting ortho–trans cycloadducts into useful synthons, which makes the approach hold great potential for organic synthesis.

Unique Steric Effect of Geminal Bis(silane) To Control the High Exo-selectivity in Intermolecular Diels–Alder Reaction

Convergent total synthesis of bryostatin 8 has been accomplished by an organosilane-based strategy. The C ring is constructed stereoselectively through a geminal bis(silane)-based [1,5]-Brook rearrangement, and the B ring through geminal bis(silane)-based Prins cyclization, thus efficiently joining the northern and southern parts of the molecule.

Total Synthesis of Bryostatin 8 Using an Organosilane-Based Strategy

[1,5]-Anion Relay/[2,3]-Wittig Rearrangement of 3,3-Bis(silyl) Allyl Enol Ethers: Synthesis of Useful Vinyl Bis(silane) Species

Geminal bis(silyl) enal: a versatile scaffold for stereoselective synthesizing C3,O1-disilylated allylic alcohols based upon anion relay chemistry.

Addition of TMS-substituted oxiranyl anions to acylsilanes. A highly stereoselective approach to tetrasubstituted (Z)-β-hydroxy-α-TMS silyl enol ethers.

Studies on retro-[1,4] Brook rearrangement of 3-silyl allyloxysilanes. Observation of the formation of unusual 3,3-bissilyl enols

Handle everyday research tasks with reliable, citation-backed results

Your personal Research Agent to handle research tasks with citation-backed results

Popular Tasks used by Researchers

How can I help with your research?

Meet SciSpace

Get more enhanced response by uploading the PDFs you want me to reference.

No relevant PDFs in your library

SciSpace is the AI research assistant for academics. Run systematic literature reviews on 280M+ papers, and write papers with cited sources. Trusted by 1M+ students, PhDs & researchers.

SciSpace | AI for Research

Analyze PDFs

Code & Manuscripts

Funding & Grants

Literature & Patents

Medical & Clinical Data

Systematic Review

Visualize & Present

Web & Data

Build a Google Scholar-like website for your research.

Build a website

Create charts and images for your research

Create a Chart

Write a paper for submission to a journal

Draft a manuscript

Patent Search

Design eye-catching scientific posters in minutes.

Scientific Poster Generation

Systematic Literature Review

One task is running at the moment. Your messages will be shown right after.

Drag and drop or click here to browse

Loved by <highlight>1 million+</highlight> researchers

Extract a list of specific topics and their sources from unstructured text

Topics

Compare and analyze relevant papers that matches with your search

Papers

Get insights from PDFs and bookmarked papers from your library

My library

Recent searches

Try searching for:

Catch AI-generated content in scholarly and non-scholarly content

{ai} Detector

Ai Writer

Get PDF Summaries, highlighted text explanations 

Chat with PDF

Effortlessly create in-text citations and bibliographies in APA and 2,500 other formats

Citation generator

Get explanations, summaries, and answers on academic papers

Ease up your research workflow with {scispace}'s cohort of exciting AI tools

Elevate your academic writing skills and convey your ideas the way you want

Paraphraser

Explore our range of reading and writing tools

Your file is being prepared and should be ready in a few minutes. If it's a large file, it might take a bit longer. You can close this window, and we'll email you the file when it's done.

You have reached a maximum limit of <strong>{limit}</strong> columns in the table. Remove at least <strong>1</strong> column to add or create another one.

Xianwei Sun

Author Tools

Chat about Author