Gold(I) Cavitands for the Assembly of Molecular Complexity

Identifier:  TDX:3832

Handle: https://hdl.handle.net/20.500.11797/TDX3832

Authors:  Martin Torres, Inmaculada

Abstract:
Gold(I)-catalyzed organic transformations have been widely developed as powerful tools for the assembly of complex molecular frameworks. This Doctoral Thesis covers three topics related to homogeneous gold(I) catalysis. First, new families of both chiral and achiral gold(I)-cavitand complexes were designed and prepared from resorcin[4]arene precursors. The achiral gold(I) complexes were applied in the cycloisomerization of 1,6-dienynes and led to uncovering of new selectivities. Furthermore, the chiral gold(I) cavitands were investigated in the enantioselective alkoxycyclization of 1,6-enynes. This method was applied to the total synthesis of (+)-mafaicheenamine C. Second, new types of non-acceptor carbene precursors were developed. These allowed to carry out gold(I)-catalyzed decarbenations of persistent cyclopropanes, releasing polyaromatic units as driving force. Following this methodology, a variety of cyclopropanes could be obtained upon release of naphthalene or phenanthrene. Finally, the ability of gold(I) complexes to construct polycyclic architectures was demonstrated by devising a novel approach for the synthesis of decalins from the polyenyne cyclization of tetrasubstituted silyl enol ethers. The acquired decalins are key intermediates in the synthesis of the natural products.