An oxyacetamide-directed Rh(III)-catalyzed Z-type alkenyl C-H functionalization through a rare exo-rhodacyle intermediate is described, forming multisubstituted dienes and allenes. A variety of alkenes and propargylic carbonate coupling partners are suitable for this transformation with high regio- and stereoselectivity. The synthetic utility is demonstrated by the selective late-stage modification of the Z-type natural products as well as the synthesis of the unnatural β-amino acid.