A stereoselective one-pot procedure was developed to prepare S-substituted (Z)-enol esters through a base-triggered rearrangement. This transition metal-free multicomponent approach can be performed under an air atmosphere at room temperature, tolerates a wide set of chemical functionalities and generally affords high isolated yields. The (Z)-selectivity arises from the [1,4]-S- to O-acyl migration.

The synthetic scope of the reactions between benzenethiolate, 4-methoxybenzenethiolate, 2-naphthalenethiolate, and 2-pyridinethiolate anions with 1,3-dihalo-2,2-dimethylpropane was studied. These reactions render mono and disubstituted products from good to excellent yields. For all the substrates studied the monosubstituted halogenated product is the intermediate or the main product depending on the nature of the second leaving group. Aryl cyclopropyl sulfides were found as side products and their yields strongly depend on the base concentration (tertBuOK). Finally, using neopentyl iodide as a model, the mechanism of these reactions was evaluated based on non-kinetic evidence, demonstrating that the reactions switch from S RN 1 to polar S N 2 according to the solvent employed.

Using simple tert‐butoxide as base, the relatively complex five‐membered ring diketone structure of the title compounds is easily obtained under transition‐metal‐free conditions.

Stereoselective One-Pot Synthesis of -Alkylsulfide Enol Esters. Base-Triggered Rearrangement under Mild Conditions. -(HEREDIA, A. A.; SORIA-CASTRO, S. M.; BOUCHET, L. M.; OKSDATH-MANSILLA, G.; BARRIONUEVO, C. A.; CAMINOS, D. A.; BISOGNO, F. R.; ARGUEELLO, J. E.; PENENORY*, A. B.; Org. Biomol. Chem. 12 (2014) 33, 6516-6526, http://dx.