The preparation and oxidation of disulfides as a route to sulfone-sulfides

Abstract

Mercaptide/alkoxide competition in substitution and addition reactions is discussed as it applies to the preparation of disulfides. Oxidation of an asymmetric disulfide with H2O2 is shown to exhibit high regioselectivity which may be rationalized in the same terms employed for other sulfide oxidations, viz. substituent electron withdrawing ability (Xp) and steric effects.

Investigation of Synthetic Routes towards Derivatives of 3-(Phenylsulfonimidoyl)propanoic Acid

“…Reaction of PhSNa with methyl acrylate according to the procedure of Ahern et al [4] in MeOH resulted in the formation of the desired sulfide 3 in a disappointing yield. The major product 4 of the reaction was the result of competing addition of MeOH to the electrophile.…”

Total synthesis of the antibacterial polyketide natural product thailandamide lactone

“…However, DMP without NaHCO 3 produced the required product 5 in 73% yield. The appearance of a signal at a d of 15.6 ppm in the 1 H NMR spectrum of compound 5 and two carbonyl carbons at d 183.0, 183.9 ppm in its 13 C NMR spectrum clearly ascertained its existence as keto-enol tautomeric mixtures.…”

“…11 The synthesis of intermediates 7 and 8 is depicted in Scheme 3. The known vinyl iodide 19, 12 prepared from propargylic alcohol using the Negishi reaction as the key step, was subjected to the Mitsunobu reaction using 1-phenyl-5-thiotetrazole (15) and the resultant sulde was oxidized using (NH 4 ) 6 -Mo 7 O 24 $4H 2 O/H 2 O 2 in dioxane 13 to access sulfone 20. Notably, the production of sulfone 20 from its corresponding sulde was found to be much more efficient in dioxane than in the commonly used ethanol.…”

“…However, DMP without NaHCO3 resulted the required product 5 in 73% yield. The appearance of a signal at δ 15.6 ppm in 1 H NMR and two carbonyl carbons at δ 183.0, 183.9 ppm in 13 The completion of total synthesis of thailandamide lactone is depicted in Scheme 7 where the stage was set for the crucial coupling between the western (4) and eastern (5) segments. Extensive efforts were made for optimization of the Heck coupling (Table 2).…”

Chemoselective reaction of a sulfonate ester with methoxide ions in preference to benzyl mercaptide anions

“…Among many potential methodologies, this chemistry could offer "one-pot" methodologies for symmetric ethers and for sulfides. Equations [8] and [9] give preliminary results for each of these methodologies. 'O~hese calculations were carried out as part of a previously 1 published study.…”