Solistatin (41), isolated from Penicillium solitum and known to inhibit cholesterol synthesis, was previously prepared three times in 7-17 steps (57% ideality for the shortest route. Building blocks in the shortest route are also illustrated in Figure ), featuring stereoselective aldol reactions or iterative Overman esterification strategies. However, the aldol approach suffers from low diastereoselectivity (2:1), whereas the Overman approach requires multiple concession steps to set the stage for this rearrangement along with expensive chiral ligands and multiple uses of palladium. In contrast a cis-selective dDCC using the common diol unit 6-RAE completed the total synthesis in merely 3 steps (67% ideality) by quickly assembling the carbon skeleton followed by lactonization. Verbalactone (42), possessing unique activity against various Gram-positive and Gram-negative bacteria, is an interesting case for analysis as it has been prepared at least 14 different ways ranging from 7-22 step-count (57% ideality for the shortest route). Although a macrolactonization approach to unite the two symmetrical fragment is common, accessing the key fragment requires multiple concession steps regardless of the strategy employed such as a combination of dithiane chemistry and chiral epoxide opening or asymmetric allylation. Again, the radical approach described herein employs a cis-selective dDCC on 6-RAE with hexanoic acid RAE followed by deprotection of the acetonide and tert-butyl ester, delivering the key symmetrical unit in 2 steps. Avocadene (43), isolated from the avocado tree (Persea americana), exibits anticancer activity against the human prostate adenocarcinoma as well as activity in the yellow fever mosquito larvae insecticidal assay. The previous synthesis of 43 proceeded in 9 steps (44% ideality) featuring a Noyori asymmetric reduction as well as a diastereoselective reduction of a β-hydroxyketone to establish the key 1,3-diol stereochemistry. In a significant departure from this conventional logic, cis-selective dDCC on 6-RAE with 13-tetradecenoic acid RAE set the stage for a 5-step synthesis of 43. To install the third hydroxyl group of 43, another radical reaction on the remaining carboxylate, decarboxylative borylation, was enlisted followed by oxidative workup. Gingerdiol (44), isolated from ginger rhizome, was previously prepared four times in 9-15 steps (33% ideality for the shortest route), featuring polar transformations such as Keck allylation, 29 epoxide opening and iterative proline catalysed α-aminoxylation of an aldehyde. A far more intuitive approach can be realized using cis-selective dDCC of 6-RAE with a functionalized phenylpropionic acid RAE, followed by another dDCC to complete the total synthesis of 44 (5 steps, 40% ideality). The completely programmable diastereoselectivity of dDCC reactions on 6 (delivering cis-or trans-products at-will) could be also harnessed to access natural products bearing a transarrangement between diol motifs as illustrated in the next three total syntheses. For instance, streptenol B (45), a cholesterol synthesis inhibitor isolated from streptomyces species, 31 was previously prepared in 6 steps as a racemate (17% ideality) with a poor diastereoselectivity in the Grignard reaction step. Trans-selective dDCC between 6-RAE and (E)-4-hexenoic acid RAE followed by acetonide deprotection and reduction of the remaining ester afforded 45 concisely (3 steps, 33% ideality). Exserolide F (46), isolated from plant endophytic fungus of Exserohilum species, demonstrates significant antimicrobial activity and was previously prepared twice in steps (40 and 50% ideality). In both cases, substituted coumarin core was constructed via Sonogashira coupling followed by cationic cylization to furnish the lactone. In a complete departure from this strategy, the coumarin fragment could be incorporated via decarboxylative arylation after the trans-selective dDCC between butyric acid RAE and 6, halving the step-count