Abstract
Gold-catalysis, in this century, is one of the most emerging and promising new areas of research in organic synthesis. During the last two decades, a wide range of distinct synthetic methodologies have been unveiled employing homogeneous gold catalysis and aptly applied in the synthesis of numerous natural products and biologically active molecules. Among these, the reactions involving α-oxo gold carbene/α-imino gold carbene intermediates are of contemporary interest, in view of their synthetic potential and also due to the need to understand the bonding involved in these complexes. In this manuscript, we document the theoretical investigations on the regio-selectivity dependence of substitution on the gold-catalyzed cycloisomerization of o-nitroarylalkyne derivatives. We have also studied the relative stabilities of α-oxo gold carbene intermediates.
Highlights
Gold catalyzed reactions have been increasingly emerging in the literature over the past few decades (Hashmi, 2007; Pflästerera and Hashmi, 2015)
We have studied in detail the mechanistic aspects with density functional theory (DFT) and reasoned that the formation of an α-oxo metal carbenoid C occurs by the 5-exodig mode of cyclization of the nitro group on the alkyne, which subsequently undergoes a 6n-electro cyclization to isatogen
We document the DFT calculations on the [Au]catalysed complementary nitroalkyne redox process that leads to α-oxo gold carbenes B and C, especially focusing on the energies associated with oxygen transfer and carbene transfer
Summary
Gold catalyzed reactions have been increasingly emerging in the literature over the past few decades (Hashmi, 2007; Pflästerera and Hashmi, 2015). We have studied in detail the mechanistic aspects with density functional theory (DFT) and reasoned that the formation of an α-oxo metal carbenoid C occurs by the 5-exodig mode of cyclization of the nitro group on the alkyne, which subsequently undergoes a 6n-electro cyclization to isatogen In this manuscript, we document the DFT calculations on the [Au]catalysed complementary nitroalkyne redox process that leads to α-oxo gold carbenes B and C, especially focusing on the energies associated with oxygen transfer and carbene transfer. On both instances, it has been realized that the intramolecular process leading to isatogens or anthranil has exclusively taken place and the products obtained are from the reaction of the nucleophile employed with the
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