| Institution: | 1. Grupo de Lactamas y Heterociclos Bioactivos, Unidad Asociada al CSIC, Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Complutense de, Madrid, 28040 Madrid, Spain;2. Grupo de Lactamas y Heterociclos Bioactivos, Unidad Asociada al CSIC, Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Complutense de, Madrid, 28040 Madrid, Spain
Instituto de Química Orgánica General, IQOG, Consejo Superior de Investigaciones Científicas, CSIC, Juan de la Cierva 3, 28006 Madrid, Spain;3. School of Pharmacy, Tokyo University of Pharmacy and Life Sciences, 1432-1 Horinouchi, Hachioji, Tokyo, 192-0392 Japan;4. Instituto de Química Orgánica General, IQOG, Consejo Superior de Investigaciones Científicas, CSIC, Juan de la Cierva 3, 28006 Madrid, Spain |
| Abstract: | Herein, we report investigations embodying the first example of reversal of the native regioselectivity in the reaction of allenols with electrophiles. The effortlessness of C?C bond formation, mild reaction conditions, neither catalysts nor light irradiation, and exquisite selectivity, both in terms of functional-group tolerance and chemo-, site-, and stereo-selectivity, converts this trifluorosulfonylation-rearrangement sequence into an appealing protocol for the preparation of novel functionalized enones. The synthetic utility of this method has been validated by the conversion of the initially prepared bis(triflyl)enones into a variety of bis(triflyl)-functionalized molecules such as 1,3-dienes, allylic alcohols, pyrroles, pyrazoles, and chromenes. Besides, DFT calculations have provided a reliable understanding of observed selectivity. |
