With a viable method in hand for chemoselective and modular C-C coupling, execution of the blueprint outlined in Figure could be explored. Rather than pursue a tabular listing of coupling partners to illustrate functional group tolerance and geometric control (all stereoretentive), the value of the methodology was exemplified through the total or formal synthesis of 13 terpene natural products (Figure ). A range of functional groups is tolerated, including epoxides, alkynes, alcohols, free carboxylic acids, esters, ethers, ketones, enones, aldehydes, electron-rich (hetero)aromatics, -keto esters, and skipped dienes. The simplification enabled by this method is apparent in three poly-olefin precursors prepared en route to complex terpene natural products: progesterone (8), celastrol (9), and isosteviol (10). A protecting group free synthesis of progesterone precursor 8 begins with the electrochemical cross-coupling of two simple acids 4 (in situ activated) and 5 (prepared in two steps via carboiodination and oxidation). The product acid 6 was next in situ activated and coupled to a vinyl iodide bearing a free alcohol (11). Alcohol 12 was converted to the bromide (13) via Appel conditions and coupled to 2-iodo-3methylcyclopentenone using an electrochemical reaction inspired by Hansen's electrochemical conditions (See SI Tables ) to deliver the desired polyene endpoint (8) directly. In contrast, similar reported couplings have employed Suzuki conditions which required three steps to prepare a suitable trifluoroborate-containing coupling partners. This modular and intuitive approach takes place in six steps (longest linear sequence, LLS) relying on a single FGI and oxidation step without resorting to any protecting groups. In contrast, Johnson's synthesis of progesterone arrived at the target polyene in 8 steps (LLS) with two FGI's and two PG-related steps. In 2016, Dudley and coworkers published a 10-step total synthesis of progesterone which also prepares polyene 8 in six steps LLS with one FGI and one oxidation. Siegel's elegant approach to 9 leveraged a unique polyene cyclization precursor bearing a tetrasubstituted alkene and an electron rich arene. Cleverly, inherent symmetry was exploited to arrive at the polyene in 9 steps, using one FGI and one oxidation. The use of an HWE reaction led to a 6:1 mixture of E/Z isomers, highlighting the challenges associated with approaches that construct polyolefins through Wittig-like transforms. In contrast, the modular assembly approach breaks bonds adjacent to the olefins and programs the alkene geometry at the outset. The synthesis commences with in situ activation of acid 14 and electrochemical coupling with the same vinyl iodide 5 used in the synthesis of 8. The product acid 15 was subsequently activated and coupled with tetra-substituted vinyl iodide 16 bearing a reactive aldehyde to complete the formal synthesis endpoint of celastrol (9) in 5 steps.