Base-catalysed rearrangement of β-hydroxyvinylsilanes to allyl silyl ethers

Abstract

A 1,3-silyl group shift from carbon to oxygen occurs readily when ,B-hydroxyvinylsilanes are treated with catalytic amounts of sodium hydride in hexamethylphosphoric triamide, thus providing the first demonstration of the rearrangement of silicon from sp2-carbon to oxygen.

Recent Advances in Hydrometallation of Alkenes and Alkynes via the First Row Transition Metal Catalysis

“…[341] Subsequently, Sato and co-workers reported hydromagnesiation of dienes [342] and alkynes [343] using Cp 2 TiCl 2 as the catalyst, affording allylic and alkenyl Grignard reagents with high regio-and stereoselectivity (Scheme 123b). A titanium-hydride species (X2) was proposed as the key species involving in the catalytic cycles (Scheme 123c).…”

Cascade Resulting in the Reductive Ethynylation of Aldehydes: Dissection of Its Components

“…We took note that previous groups had investigated the possibility of using catalytic amounts (ca 10 mol % of KH) and α-TMS substituted allylic alcohol, seeking to accomplish allenylation. Only low yields of allene products were obtained 9,10,11. Apparently, under these conditions, the vinyl potassium species arising from the Brook step is protonated by remaining free alcohol.…”

Partial reduction of 3-heteroatom substituted 2-furoic acids: the role of an ortho group in viability and stereoselectivity

“…Proton nuclear magnetic resonance spectra (NMR) were recorded on a Gemini 200 at 200 MHz, a Varian Unity Inova 300 at 300 MHz, a Varian Unity Inova 400 at 400 MHz and a Varian Unity Inova 500 at 500 MHz. 13 C nuclear magnetic resonance spectra were recorded on a Varian Unity Inova 300 at 75 MHz, a Varian Unity Inova 400 at 100 MHz and a Varian Unity Inova 500 at 125 MHz. Chemical shifts (δ) are quoted in parts per million (ppm), downfield from tetramethylsilane.…”