The synthesis of tert-butoxyethyne (1a) and (1-adaroantyloxy)-ethyne (1b) has been performed by a three step sequence starting fron ethyl vinyl ether. Overall yields are 34 and 67%, respectively. The process is insensitive to the steric hindrance of the tertiary alcohol used and can be conveniently modified for the preparation of 1-tert-alkoxy-1-alkynes in high yield, without isolation of the intermediate 1-tert-alkoxyethyne.
