| Autor: |
Iglesias-Menduiña O; CINBIO, Departamento de Química Orgánica, Universidade de Vigo, 36310 Vigo, Spain., Novegil D; CINBIO, Departamento de Química Orgánica, Universidade de Vigo, 36310 Vigo, Spain., Martínez C; CINBIO, Departamento de Química Orgánica, Universidade de Vigo, 36310 Vigo, Spain., Alvarez R; CINBIO, Departamento de Química Orgánica, Universidade de Vigo, 36310 Vigo, Spain., de Lera AR; CINBIO, Departamento de Química Orgánica, Universidade de Vigo, 36310 Vigo, Spain. |
| Abstrakt: |
The strategy for the synthesis of the octahydronaphthalene core of natural macrolide sagamilactam has unintentionally evolved from the acyclic intramolecular (IMDA) to the transannular (TADA) Diels-Alder reaction. Lewis acid-promoted IMDA of a protected 2 Z ,8 E ,10 E -4,6,12-trihydroxy-2,8,10-decatrienal model with a diol of 4,6- anti relative configuration, as proposed by DP4+-based computational studies, afforded the cis -octahydronaphthalene diastereomer through the Re-endo approach. The 26-membered macrodiolide generated, under thermal reaction conditions, the trans -octahydronaphthalene by a double TADA reaction along the desired Si-exo orientation. |
