Solution and flash vacuum pyrolyses of 3-arylpropanesulfonyl and 2-(aryloxy)ethanesulfonyl azides. Synthesis of 7- and 8-membered sultams

Abstract

Products of the Reaction of 2a and la with 2-Methyl-2propanethiol. Selenenic anhydride 2a (0.29 g, 0.70 mmol) was dissolved in 15 mL of dioxane. To this was then added 0.5 mL of a 3 M solution of 2-methyl-2-propanethiol (1.40 mmol) in dioxane and 0.515 mL of 0.97 M aqueous perchloric acid, followed by enough water to bring the final volume of the solution to 25 mL. The solution was allowed to stand at room temperature. Periodically 2.5-µ aliquots were removed and diluted to 3.0 mL with 60% dioxane, and their ultraviolet spectrum was scanned between 320 and 460 nm. When the scan indicated that the reaction was complete, the solution was poured into 100 mL of water and extracted three times with 10-mL portions of chloroform. The chloroform was dried (Na2S04), the solvent was removed under reduced pressure at room temperature, and the residue was subjected to an oil pump vacuum for several hours to remove the last traces of solvent and dioxane. The residue, a yellow oil, was shown by TLC to consist of a single compound that was identified as tert-butyl o-nitrobenzeneselenenyl sulfide, í-BuSSeC6H4N02-o, 0.39 g (94%): NMR (CDC13) S 7.2-S.5 (m, 4 ), 1.38 (s, 9 H); mass spectrum, m/e 291 (M+, "Se), 289 (M+,

Discovery of Ecopladib, an Indole Inhibitor of Cytosolic Phospholipase Α2α

“…Methyl 4-{2-[1-Benzhydryl-5-chloro-2-({[(2-phenylethyl)sulfonyl]amino}methyl)-1 H -in dol-3-yl]ethoxy}benzoate (21b). Amine 17 (0.22 g, 0.40 mmol) underwent sulfonylation using the general Schotten−Baumann procedure with 2-phenylethanesulfonyl chloride , (0.14 g, 0.68 mmol) for 1 h. Flash chromatography (20 → 30% EtOAc−hexanes) of the crude sulfonamide afforded 21b (0.152 g, 52%) as a white foam. 1 H NMR (400 MHz, CDCl 3 ) δ 2.92−3.09 (m, 2 H), 3.13−3.28 (m, 4 H), 3.84−3.92 (m, 3 H), 4.23 (t, J = 5.9 Hz, 2 H), 4.30−4.41 (m, 3 H), 6.55 (d, J = 8.6 Hz, 1 H), 6.84−6.96 (m, 3 H), 7.04−7.11 (m, 5 H), 7.13 (s, 1 H), 7.21−7.34 (m, 10 H), 7.54 (d, J = 1.8 Hz, 1 H), 7.97 (d, J = 9.1 Hz, 2 H).…”

“…Amine 17 (0.22 g, 0.40 mmol) underwent sulfonylation using the general Schotten-Baumann procedure with 2-phenylethanesulfonyl chloride 57,58 (0.14 g, 0.68 mmol) for 1 h. Flash chromatography (20 f 30% EtOAc-hexanes) of the crude sulfonamide afforded 21b (0.152 g, 52%) as a white foam. 1…”

“…Amine 32b (0.200 g, 0.37 mmol) underwent Schotten-Baumann sulfonylation with 2-phenylethanesulfonyl chloride 57 (0.140 g, 0.68 mmol) according to the general procedure for 1 h. Flash chromatography (25% EtOAc-hexanes) of the crude product afforded 40e (0.210 g, 81%) as a pale yellow foam. 1…”

Flash Vacuum Pyrolysis of Azides, Triazoles, and Tetrazoles

“… In further work, seven-membered ring sultams 371 were obtained in yields of 23–27% by FVP of aralkylsulfonyl azides 370 (eq ). The mesityl derivative 372 afforded an 88% yield of the sultam 373 , where a methyl group shift has occurred (eq 68 ). …”

Synthesis of methyl 2-aryl-5-chlorosulfonyl-1,3-oxazole-4-carboxylates and their reactions with amines and amidines

“…The formation of 6H,7H-[1,3]oxazolo-[5,4-d]pyrimidin-7-ones could be rationalized as a result of transformation of the seven-membered ring B into a six-membered cycle through elimination of sulfur dioxide. Generally, such transformation occurs under severe conditions [18,19]. Therefore, in the studied case the more likely opportunity was the intramolecular rearrangement of the products A of amidines N-sulfonylation into the intermediates C via attack at the C 5 atom of oxazole ring with nucleophilic nitrogen atom.…”