The functionalization of C-C triple bonds using p-acid catalysis has become a hugely successful area of organic synthesis, allowing the generation of complex carbo- and heterocylic frameworks in a single step.1 An important class of p-acid catalyzed reactions are carboalkoxylations and related processes in which attack of a heteroatom nucleophile onto an alkyne precedes migration of a suitable group. These reactions can evolve along different pathways, affording highly functionalized materials.2In this talk I will discuss the use of ynamides to control the regioselectivity and evolution of these carboalkoxylation processes in order to access alternative reaction outcomes.I will demonstrate how this strategy has been realized in the formation of highly functionalized indenes from simple ynamides under gold catalysis. A 1,1-carboalkoxylation likely generates a gold carbene intermediate which is quenched by a 1,2-regioselective migration of the amide group. This process represents a rare example of C-N cleavage of the ynamide moiety and generates new C-O, C-N and C-C bonds in a single step. The versatility of gold carbene intermediates allows further diversity of products to be realized which will be discussed.a) A. S. K Hashmi, Angew. Chem. Int. Ed., 2006, 45  , 7896. (b) A. F�rstner, P. W. Davies, Angew. Chem. Int. Ed., 2007, 46  , 3410. c) H. Huang, Y. Zhou, H. Liu, Beilstein. J. Org, Chem., 2011, 7  , 897.H. V. Adcock, P. W. Davies, Synthesis, 2012, 44  , 3401.

Gold catalyzed carboalkoxylation: Harnessing the divergent reactivity of ynamides

248th National Meeting (2014)

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