The efficient and highly selective formation of a wide range of (hetero)cyclic cis-diol scaffolds using powerful aminotriphenolate- based metal catalysts is reported. The key intermediates are cyclic carbonates that are derived in high yield and with high levels of diastereo- and chemo-selectivity from the parent oxirane precursors and carbon dioxide (CO2). Deprotection of the carbonate structures affords synthetically useful cis-diol scaffolds with different ring sizes incorporating various functional groups. This atom-efficient methodology allows for simple construction of diol synthons using cheap and accessible precursors and green metal catalysts, and showcases the use of CO2 as a temporary protecting group.