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Cobalt-assisted Medium Ring Cyclization for Solanoeclepin A and Taxoid Synthesis
Dissertation

Cobalt-assisted Medium Ring Cyclization for Solanoeclepin A and Taxoid Synthesis

Lin, Ya-Ting
Doctor of Philosophy (PHD), 國立清華大學, 化學系
2014

Abstract

紫杉醇 八羰基二鈷 尼古拉斯反應 細見-櫻井反應 普林斯羰基-烯反應 Taxol dicobalt hexacarbonyl Nicholas reaction Hosomi-Sakurai reaction Prins-Carbonyl-ene reaction
The synthesis of Taxol 1 and Solanoeclepin A 148 has been attracted chemist’s attention in recent three decades, due to the challenge to construct those poly-carbocyclic sub-structures. Taxol 1 and its derivatives 2, 3, and 4 are known as the potent agents against a wide range of tumor cells. Solanoeclepin A 148, on the other hand, shows a significant hatch-stimulating activity towards the potato cyst nematodes. In this thesis, we have focused on the construction of twelve-membered carbocyclic substructure and seven-membered carbocyclic substructure of bicylic tetraene 25 and tetracyclic diene 231, respectively. The complexation of dicobalthexacarbonyl group played important roles not only in bending the molecule to suitable orientation to bring the moieties closer, but also using Nicholas effect and further Hosomi-Sakurai reaction and Prins-ene/halo reaction induced by Lewis acid to complete the synthesis of tetraene 25 and diene 231 frameworks.

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