Gold double intramolecular

Apart from these two examples, in the rest of the olefin activations, gold coordinates to the olefin, turning it susceptible to nucleophilic attack. The early examples of alkene functionalization by gold catalysis (equation 144) focused on the intermolecular addition of 1,3-diketones to styrenes. " An intramolecular version with ketoamides to yield pyrrolidinones was later developed and followed by the intermolecular addition of phenols (equation 145) and carboxylic acids to double bonds,a work that included an example of intramolecular addition of an aliphatic alcohol to an olefin. 

Hydroamination. On complexing to (/J)-xylyl-BINAP gold p-nitrobenzoate activates a double bond of an aUene moiety to allow intramolecular attack by an amino group, asymmetrically. 

Very recently, the enantio- and diastereoselective synthesis of an S-shaped double azahelicene has been achieved via the gold-catalyzed sequential intramolecular alkyne hydroarylation (Scheme 21.51) [57]. 

Intramolecular additions of alcohols or amines to olefins are recognized as useful methods to provide heterocyclic compounds. Kozmin and Zhang have achieved a gold-catalyzed synthesis of heterobicyclic alkenes by double cyclization of alcohols or sulfonamides which have a 1,5-enyne moiety [175]. As a typical example, unsaturated alcohol (95) is smoothly converted to 6-oxabicyclo[3.2.1]octane (96) in 90% yield using a 5 mol% of AuCls catalyst (Scheme 18.34). Cyclic ethers are also available from homopropargylic ethers with pendant alcohols through gold-catalyzed... 

A detailed study of the enantioselective gold-catalysed allylic alkylation of substituted indoles (1) forming tertrahydrocarbazoles has been investigated both experimentally and theoretically at the B3LYP/LDBS level of theory. The results indicate that the reaction 0 occurs by an intramolecular 5n2 attack by C(2) of the indole ring on the double bond... 

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