Gold(I)-Catalyzed [8+2]-Cycloaddition Of 8-Aryl-8-Azaheptafulvenes With Allenamides And Ynamides: Regioselective Synthesis Of Dihydrocycloheptapyrrole Derivatives

Gold(I)-catalyzed higher-order [8+2] cycloadditions of 8-aryl-8-azaheptafulvenes 1 with allenamides 2 and ynamides 3 were studied. 1,8-Dihydrocycloheptapyrroles 4 were achieved by a regioselective [8+2] cycloaddition of azaheptafulvenes 1 and allenamides 2 in the presence of (2,4-ditBuC(6)H(3)O)(3)PAuNTf2 as catalyst. Besides, ynamides 3 and 8-aryl-8-azaheptafulvenes 1, undergo a regioselective [8+2] cycloaddition, to give 2-amido-1,4-dihydrocycloheptapyrroles 7 in the presence of JohnPhosAuNTf(2) as catalyst. Both reactions take place with good yields and with a variety of substituents. A plausible mechanism hypothesis suggests a nucleophilic attack of the 8-azaheptafulvene to the gold activated electron rich allene or alkyne moieties of the allenamide and ynamide, respectively.