A Desilylation and a One-Pot Desilylation−Oxidation of Aliphatic tert-Butyldimethylsilyl Ethers Using Catalytic Quantities of PdCl₂(CH₃CN)₂

Reactions at Oxygen Atoms

“…The TBDMS and triisopropylsilyl (TIPS) ethers are catalytically desilylated with PdCI 2 (MeCNh by heating (6 h, 75 ·C) in acetone (or 1:1 acetone/DMF) containing 5 equiv of water [175] (oxidation mechanism). TBDMS ethers are also cleaved to the corresponding alcohols by the action of N-bromosuccinimide (NBS) in aqueous DMSO [176]; the mechanism is not clear; however, it is considered to be caused by the slow release of bromine from NBS.…”

Dichloro Bis(acetonitrile) Palladium

“…Interestingly, a modified procedure has been developed for the one-pot desilylationoxidation of aliphatic tert-butyldimethylsilyl ethers using catalytic quantities of PdCl 2 (CH 3 CN) 2 , which provides aldehydes and ketones in good yields (eq 48). 84 The hydrolysis of enol ethers, 85 enol esters, 85 and acetals, 81 to the corresponding carbonyl compounds also proved to be efficiently catalyzed by PdCl 2 (CH 3 CN) 2 . (48) Isomerization of cis-Arylalkenes to trans-Arylalkenes.…”

Mono and dibromo-5,5-diethylbarbituric acids for cleavage of trimethylsilyl ethers

“…4,5 Although there are many new reports on the protection and deprotection of silyl ether groups, [6][7][8][9][10][11][12][13][14][15][16][17][18][19] only a few procedures for the oxidative deprotection are known. [20][21][22][23][24][25][26][27][28] Some of these procedures utilize expensive and hazardous reagents, Lewis acid catalysts, need long reaction times, afford low yields, and need tedious work up. Thus, there is still a need for developing mild and eco-friendly procedures for the oxidative deprotection of trimethylsilyl ethers.…”