In this Doctoral Thesis, new families of both chiral and achiral gold(I)-cavitand complexes have been designed and prepared from resorcinarene precursors. The achiral gold(I) complexes were applied in the cycloisomerization of 1,6-dienynes and led to uncovering of new selectivities. On the other hand, the chiral gold(I) cavitands allowed to develop a broad-scope enantioselective alkoxycyclization of 1,6-enynes, which was applied to the first total synthesis of (+)-mafaicheenamine C. New types of non-acceptor carbene precursors were also developed. These precursors allowed to carry out gold(I)-catalyzed decarbenations of persistent cyclopropanes, releasing polyaromatic units as driving force. Following this methodology, a variety of cyclopropanes were 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 by polyenyne cyclization of tetrasubstituted silyl enol ethers. The obtained decalins are key intermediates in the synthesis of the natural products.
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