Ether Fission of 2,5-bis(Dialkylamino)hydroquinone Dimethylethers and O-Alkylation of 2,5-bis(Dialkylamino)hydroquinones

In connection with work underway in these laboratories on the total synthesis of Pentacyciic. triterpenes; guitable methods were sought for the introduction of angular methyl groups into preiormed polynuclear systems. A method of some generality was recognized in the work ofNagata³ on the organoaluminum catalyzed conjugate addition of cyanide to α,β-unsaturated ketones and subsequent conversion of the resulting cyano group to the desired angular methyl substttuent. The total synthesis of dl-alnusenone reported^4a earlier from these laboratories has this synthon as its central feature. Another approach that appeared attractive entailed the 1,6-addition ⁵ of cyanide to the dienone 1, available from intermediates already in hand.^4b