The conjugated entriyne natural product, (S)-(E)-15,16-dihydrominquartynoic acid (1), is synthesized in five linear steps and 30% overall yield from the known aldehyde 11. The key step is a one-pot in situ desilylation/Cadiot-Chodkiewicz coupling reaction affording the entriyne unit. The bromoalkyne 6 with an omega-carboxylic acid group was found to undergo a copper-catalyzed cross-coupling rea...

A single clean, good-yielding, environment-friendly microwave-assisted procedure for O-silylation of uridine with tert-butyldimethylsilyl chloride (TBDMSCl), 1,8-Diazabicyclo(5.4.0)undec-7-ene (DBU) and potassium nitrate as catalyst under solvent-free conditions is reported. Subsequent silyl ether deprotection accomplished a reusable acidic resin via microwave irradiation. Both the silylation d...

The total synthesis of the endogenous inflammation resolving eicosanoid resolvin D2 (1) is described. The key steps involved a Wittig reaction between aldehyde 5 and the ylide derived from phosphonium salt 6 to give enyne 17 and condensation of the same ylide with aldehyde 7 to afford enyne 11. Desilylation of 11 followed by hydrozirconation and iodination gave the vinyl iodide 4 and Sonogashir...

Quaternisation of 3,5-diaryl-1,2,4-thiadiazoles with trimethylsilylmethyl triflate at 40 8C occurred at N-2. Separate desilylation of the salts resulted in a ring expansion to substituted 2H-1,3,5-thiadiazines 5. Heating of these with ethanolic sodium ethoxide caused sulfur extrusion and ring contraction to 2,4-disubstituted imidazoles 6. 3,4-Diaryl1,2,5-thiadiazoles were less reactive to alkyl...

A concise enantioselective synthesis of the advanced intermediate 5 for the synthesis of pumiliotoxins (Gallagher's intermediate) is described. The synthesis started from the regio- and trans-diastereoselective (dr = 98:2) reductive 3-butenylation of (R)-3-(tert-butyldimethylsilyloxy)glutarimide 14. After O-desilylation and Dess-Martin oxidation, the resulting keto-lactam 10 was subjected to a ...

Clickable oligonucleotides with ethynyl residues in the 5-position of pyrimidines ((eth)dC and (eth)dU) or the 7-position of 7-deazaguanine ((eth)c(7)G(d)) are hydrated during solid-phase oligonucleotide synthesis and workup conditions. The side products were identified as acetyl derivatives by MALDI-TOF mass spectra of oligonucleotides and by detection of modified nucleosides after enzymatic p...

An efficient approach to a novel family of (Z)-3-amino-3-oxo-1-propenyl selenocyanates was developed based on the reaction KSeCN with 3-trimethylsilyl-2-propynamides in presence ammonium chloride methanol. The accompanied by desilylation process. products were not formed under same conditions absence chloride, which used for first time reactions acetylenes. use this new methodology allowed carr...