An unprecedented cascade vinylogous Mukaiyama 1,6-MA/MA of 2-silyloxyfurans and azoalkenes was realized with a Cu(II)/Bu-t-Box complex. An array of fused butyrolactones containing multiple stereocenters was generally obtained in good yield (up to 90% yield) with exclusive diastereoselectivity (>20:1 dr) and excellent enantioselectivity (up to 99% ee). Carbon isotope effects measured by C-13 NMR revealed a stepwise mechanism for this annulation process.