Biomimetic total synthesis of bisorbicillinol, bisorbibutenolide, trichodimerol, and designed analogues of the bisorbicillinoids

The bisorbicillinoids are a growing class of novel natural products endowed with unique biological activity and are associated with fascinating hypoth eses for their biosynthesis. A full account of our biomimetic explorations toward the bisorbicillinoids including the total syntheses of bisorbicillin ol (1), bisortibutenolide (2), and trichodimerol (4) from sorbicillin (3) i s disclosed. Utilizing the novel dimerization reactions discovered and fine -tuned en route to 1 and 4, several analogues of these natural products hav e been synthesized. Furthermore, studies on the scope of these novel cycloa ddition reactions and the isolation of a number of unexpected products alon g with proposed mechanisms for their formation are reported. These findings add to our knowledge of the largely unexplored chemistry of o-quinols and related aromatic systems.