| Sumario: | To achieve high asymmetric selectivities and high efficiency in biomimetic cationic polyene cyclization is a challenging problem in both academia and industries. The intramolecular acetal-initiated cationic polyene cyclization reaction was first introduced and well developed by W. S. Johnson. However, there exist some disadvantages in this intramolecular polyene cyclization. The need to incorporate the required acetal into the acyclic precursor added synthetic complexity. In addition, the accommodation of the acetal moiety also diminishes the structural flexibility in the acyclic precursor. These two problems, though minor, could reduce the scope and applicability of the method substantially. The emphasis of this thesis is placed on the evolution of a novel intermolecular acetal-initiated polyene cyclization reaction to overcome these current limitations and manifestation of its applicability on the asymmetric total synthesis of natural products.
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