Reaction of a beta-(1 --> 4) linked galactan with TDMS chloride followed by methylation and desilylation yields methyl galactans with unconventional functionalization patterns. The products were characterized via FTIR and NMR of the intact polymer and by CE after controlled depolymerization. A TDMS-derivatized methyl galactan contains differently methylated secondary hydroxyl groups. SEC and an...

A new efficient method for deprotection of TBDMS derivatives of phenols, primary alcohols, carboxylic acids and secondary amines, consisting of SbCl5 and MeCN with 0.1% water (w/v), is reported. It effects inter alia desilylation of a CH2OTBDMS group in the presence of a ketal function. © 2003 Elsevier Ltd. All rights reserved. The application of silyl groups as protecting groups for O, N, S, e...

A versatile synthesis of 1,2,3-triazolyl-4-phosphines from the borane complexes of phosphino-alkynes is reported. The efficiency of the procedure relies on the use of readily available silyl-protected alkynylphosphine-boranes, which were subjected to desilylation with TBAF followed by copper-catalyzed azide-alkyne-cycloaddition in one pot. Subsequent treatment with DABCO afforded the targeted t...

Vinylogously extended deoxyeritadenine derivatives were synthesized as acyclic/ carbocyclic analogues of the 6'-halo(homovinyl)adenosines, which are known to be potent inhibitors of S-adenosyl-L-homocysteine hydrolase. Swern oxidation of 9-[3-(t-butyldimethylsilyloxy)-4-hydroxybutyl]adenine (4) followed by Wittig olefination and desilylation gave access to ethyl 6-(adenin-9-yl)-4-hydroxy-2(E)-h...

We describe a titanocene(III)-catalyzed deuterosilylation of epoxides that provides β-deuterated anti-Markovnikov alcohols with excellent D-incorporation, in high yield, and often diastereoselectivity after desilylation. The key to the success reaction is novel activation method Cp2TiCl2 (tBuC5H4)2TiCl2 BnMgBr PhSiD3 provide [(RC5H4)2Ti(III)D] without isotope scrambling. It was developed discov...

A systematic study of the Diels–Alder reaction α-nitrocinnamate was performed. The p-substituted with 2,3-dimethyl-1,3-butadienes smoothly proceeded regardless p-substituent, which either an electron-donating or -withdrawing group. control revealed that isomerized during reaction. Danishefsly’s diene (1-methoxy-3-trimethylsiloxy-1,3-butadiene) facilitated cycloaddition under mild conditions to ...

Lithium trimethylsilyldiazomethanide and a cobalt (II) precursor with an N-anchored tris-NHC (TIMENmes ) ligand provide access to the nitrilimide 1. Complex 1 was structurally characterized by single-crystal X-ray diffractometry (SC-XRD) its electronic structure examined in detail, including EPR spectroscopy, SQUID magnetometry computational analyses. The desilylation of C-(trimethylsilyl)nitri...