Trifluoromethanesulfonyl Chloride Research Articles

ChemInform Abstract: STUDIES ON NUCLEOSIDES AND NUCLEOTIDES. LXXXVII. PURINE CYCLONUCLEOSIDES. XLII. SYNTHESIS OF 2′‐DEOXY‐2′‐FLUOROGUANOSINE

AbstractAuf dem im Formelschema angegebenen Weg wird das fluorhaltige Nucleosid (IX) hergestellt.

Studies on nucleosides and nucleotides. LXXXVII. Purine cyclonucleosides. XLII. Synthesis of 2'-deoxy-2'-fluoroguanosine.

2'-Deoxy-2'-fluoroguanosine (VII) was synthesized starting from 8, 2'-anhydro-8-oxy-9-β-D-arabinofuranosylguanine (8, 2'-O-cycloguanosine) (I). Compound I was protected at 2-NH2 with an isobutyryl group and at 3'- and 5'-OH with tetrahydrofuranyl groups. The protected compound III was derivatized to the arabino nucleoside V and thence converted to VII by treatment with trifluoromethanesulfonyl chloride and tetra-n-butylammonium fluoride. The resulting 2'-deoxy-2'-fluoroguanosine showed a 3'-endo favored conformation.

Synthetic Methods and Reactions; 721. Mild Fragmentative C-C Bond Cleavage of α-Hydroxyketoximes with Trifluoromethanesulfonic Anhydride, Trifluoroacetic Anhydride, or Trifluoromethanesulfonyl Chloride.

Synthetic Methods and Reactions; 72¹. Mild Fragmentative C-C Bond Cleavage of α-Hydroxyketoximes with Trifluoromethanesulfonic Anhydride, Trifluoroacetic Anhydride, or Trifluoromethanesulfonyl Chloride.

Some reactions of 10-substituted-10H-pyrido[3,2-b][1,4]benzothiazine-n-butyllithium adducts with acyl and sulfonyl chlorides

Reaction of 10H-pyrido[3,2-b][1,4]benzothiazines 1 possessing a 10-methyl 1f, 10-(3-dimethylaminopropyl) 1b, or 10-(2-dimethylaminopropyl) 1c substituent, with n-butyllithium and methyl chloroformate or diethyl chlorophosphate affords predominantly 1,2-dihydropyridines 11 and the 4-substituted derivatives 12. The 1,7-disubstituted product 15b was obtained from reaction of the 10-methyl compound 1f with p-fluorobenzoyl chloride. On the other hand, treatment of the 10-methyl analog 1f with trifluoromethanesulfonyl chloride gave the unexpected 4-chloro derivative 12c and 13c which probably arises from the 1-trifluoromethanesulfonyl-1,2-dihydropyridine 11c via elimination of trifluoromethanesulfonic (sulfinic) acid. The N-10 dealkylated product 1a was obtained from reaction of the 10-(1-methyl-2-dimethylaminoethyl) analog 1g with n-butyllithium and methyl chloroformate, whereas a similar reaction employing the 10-(2-dimethylaminoethyl) derivative 1h gave rise to the N-methoxycarbonyl derivative 18. On the other hand, reaction of 1h with n-butyllithium alone gave the N-10 n-hexyl product 19. Mechanisms for the formation of 1a, 11, 12, 13, 15, 16, and 19 are described.

Reaction of trifluoromethanesulfonyl chloride with dialkyl hydroxyalkylmalonates. A synthesis of 2,2,-disubstituted tetrahydrofurans, pyrans and pyrrolidines

Diethyl 2-(ω-hydroxypropyl or butyl) malonates are shown to give 2,20dicarbethoxytetrahydrofuran or tetrahydropyran, when allowed to react with CF 3SO 2Cl/NEt 3 in CH 2Cl 2.

Preparation and characterization of five and six-coordinated iridium(III) complexes containing S-, O- or O,O′-trifluoromethanesulfinato groups

The oxidative addition of trifluoromethanesulfonyl chloride to trans-{IrX-(CO)[P(C 6H 5) 3] 2} yields as the only product an iridium(III) complex, {IrXCl-(OS(O)CF 3)(CO)[P(C 6H 5) 3] 2} (Ia, X  Cl; Ib, X  Br) in which the O-sulfinato group is trans to the carbonyl ligand. This is in contrast to the behavior of hydrocarbon sulfonyl halides which have previously been found to give exclusively S-bonded forms with the sulfinato group trans to chloride. The S- and O,O′-trifluoromethanesulfinato isomers of the compound {IrCl 2(O 2SCF 3)[P(C 6H 5) 3] 2} have been prepared and characterized. Addition of carbon monoxide or pyridine to either of these isomers gives {IrCl 2(-S(O) 2CF 3)[P(C 6H 5) 3] 2 · B} (B  CO or C 5H 5N) in which the added Lewis base is trans to an S-sulfinato group.