RESUMEN
A fluorination-induced intramolecular cyclization for the synthesis of fluoro-substituted spiro-1,3-oxazine and spiro-1,3-thiazine derivatives is described. N-(2-(Cyclohex-1-en-1-yl)ethyl)benzamide and benzothioamide are used as the substrates, and the cationic fluorinating agent Selectfluor works as the fluoride source. The reaction yields a single diastereomer. The scope of this regioselective fluorination reaction is established by preparing thirty different spirooxazine and spirothiazine derivatives.
RESUMEN
A three-component domino Knoevenagel-hetero-Diels-Alder (DKHDA) reaction between 1,3-dicarbonyl, aldehydes/ketones, and alkenes/alkynes leading to the divergent synthesis of chromenones, dihydrochromenones, and spirocyclic chromenones is reported. The reaction was carried out under solvent-free conditions using a magnetically separable silica (Fe3O4@SiO2) catalyst. While two component DKHDA reactions are known, this is the first example of a three component DKHDA reaction involving 1,3-dicarbonyl, ketones, and alkynes producing spirocyclic pyranone derivatives. Twenty-six different highly substituted chromenones were synthesized using this methodology. A wide substrate scope due to the multicomponent nature of the reaction, high atom economy, the use of inexpensive and non-toxic recyclable silica as the catalyst, and solvent free reaction conditions make it an advantageous process. The catalyst was characterized using different analytical techniques such as XRD, IR, HRTEM, VSM, and TGA. Based on the earlier reports a mechanism has also been proposed.