No abstract

Alkylgold(I) complexes were formed from the gold(I)-promoted intramolecular addition of various amine nucleophiles to alkenes. These experiments provide the first direct experimental evidence for the elementary step of gold-promoted nucleophilic addition to an alkene. Deuterium-labeling studies and X-ray crystal structures provide support for a mechanism involving anti-addition of the nucleophile to a gold-activated alkene, which is verified by DFT analysis of the mechanism. Ligand studies indicate that the rate of aminoauration can be drastically increased by use of electron-poor arylphosphines, which are also shown to be favored in ligand exchange experiments. Attempts at protodeauration lead only to recovery of the starting olefins, though the gold can be removed under reducing conditions to provide the purported hydroamination products.

No abstract

In control: Gold(I)‐catalyzed intramolecular addition of silyl enol ethers to alkynes and allenes allows for the diastereoselective synthesis of cyclopentenes with control of the position of the double bond. The utility of these reactions is demonstrated by an efficient total synthesis of (+)‐lycopladine A that takes advantage of the orthogonal reactivity of AuI and Pd0 towards unsaturated iodides (see scheme).

Chiral ligands (L*) and chiral anions [(S)-TriPAg] are employed in the gold(I)-catalyzed enantioselective intramolecular additions of hydrazines and hydroxylamines to allenes. These complementary methods allow access to chiral vinyl isoxazolidines, oxazines, and differentially protected pyrazolidines. PNB=para-nitrobenzoy