An efficient multicomponent reaction for the synthesis of stereoenriched cyclopentyl-isoxazoles from camphor-derived α-oximes, alkynes, and MeOH is reported. Our method involved a series of cascade transformations, including the in situ generation of an I catalyst, which catalyzed the addition of MeOH to a sterically hindered ketone. Oxidation of the oxime, and rearrangement of the α-hydroxyiminium ion generated a nitrile oxide in situ, which, upon [3+2] cycloaddition reaction with an alkyne, delivered the regioselective product. This reaction was very selective for the syn-oxime. This multicomponent approach was also extended to the synthesis of a new glycoconjugate, camphoric ester-isoxazole C-galactoside.