The power of such a strategy for synthesis can be exemplified when considering the synthesis of polyrhacitide A (Figure ). This polyketide has the typical stereochemical array of 1,3-diol motifs; such structures have been made on countless occasions using classic 2e -synthetic strategies. As such, an iterative sequence of olefin/carbonyl chemistry involving allylation/ozonolysis/HWE/oxa-Michael is employed to construct the carbon framework with the requisite oxygen functionalities (key intermediate 4). This conventional approach is the result of decades of groundbreaking studies in polyketide synthesis to exquisitely control the stereochemical outcomes of C-C and C-O bond formation. However, one lingering drawback of this strategy is the many concession steps required to manipulate functional groups and adjust appropriate oxidation states. In stark contrast, a radical retrosynthetic approach to 4 could employ dDCC to sidestep many of these issues. Simply cutting bonds that lead to most accessible carboxylic acids results in a logical disconnection, thereby permitting only two simple commercially available acids to be stitched together, intuitively arriving at 4. In principle, only three C-C bond formation steps would be required without additional C-O bond formations or redox manipulations from octanoic acid and the key building block 6, an inexpensive 1,3-diol used to make statin-based medicines. (A) A complex interplay of chemo-, regio-and stereochemical considerations is inevitable in classical 2e-disconnection, whereas 1e -logic provides a straightforward disconnection as carbon radicals can be generated at any position. (B) A striking departure from conventional synthesis by employing radical disconnection. Three intuitive radical couplings could assemble polyrhacitide A, which was previously synthesized via common 2e -synthetic strategies. To achieve such an aspirational goal, dDCC needs to be successful on α-functionalized carboxylic acid with high diastereoselectivity.