Versatile method for introduction of bulky substituents to alkoxychlorosilanes

Palladium-Catalyzed Cross-Coupling of Silyl Electrophiles with Alkylzinc Halides: A Silyl-Negishi Reaction

“…Unfortunately, these reactions suffer from low yields, long reaction times, and significant side reactions . Alkylations with primary and aryl nucleophiles are known. , As has been recently noted, the addition of secondary organometallic reagents to silyl electrophiles is rarely effective. , In fact, to our knowledge, over the past 70 years only five isolated examples with secondary nucleophiles have been reported in the chemical literature . This is due to the lack of reactivity or competitive reductive processes with these more sterically demanding and electron-rich nucleophiles.…”

Controlled introduction of allylic group to chlorosilanes

“…Currently the most practical method for the synthesis of trisubstituted allylsilanes is a Grignard type reaction of chlorosilanes with allylmagnesium chloride, but other approaches could provide important advantages [8]. For example, the use of more reactive organolithium reagents rather than Grignard reagents, affords the trialkylsilane with bulky substituents [9]; the electrolysis of appropriate chlorosilanes gives the symmetrical difunctional disilanes in good yield [10]; palladium with SmI 2 -HMPA system catalyzed stereoselective synthesis of allylsilanes [11].…”

Harnessing open-source technology for low-cost automation in synthesis: Flow chemical deprotection of silyl ethers using a homemade autosampling system

“…The outlet from the system was collected for 60 min. The product, which was free of any pTsOH residue, as determined by 1 H and 13 C NMR spectroscopy, was isolated in 95% yield simply by removing the solvent and silicon containing by-products under reduced pressure using a rotary evaporator followed by an Edwards vacuum pump (tertbutyldimethylsilyl methyl ether, the presumed major silyl byproduct, is relatively volatile with a reported boiling point of 117 °C at atmospheric pressure 14 ).…”