In contrast, the 1e -disconnection is identified by simply selecting the most readily available building blocks and coupling them using reductive Kolbe heterocoupling, thereby deleting nearly all extraneous concession steps. Such a tactic is particularly valuable for the formation of seemingly distal stereocenters, as a myriad of chiral carboxylic acid building blocks can be easily purchased. In this way, expensive catalytic asymmetric methods and chiral auxiliaries which generally require at least three more steps (installation, diastereoselective reaction and removal) can be avoided (8, 10, 14, 22). A particularly striking example of this concept involves the enantiodivergent synthesis of insect pheromones (R)-and (S)-33, previously prepared in 11-12 steps (7-8% overall yield) using a category (i) and (ii) approaches for assembling the main carbon chain (vide supra). In contrast, commercially available desymmetrized acid 30 can be subjected to tandem reductive Kolbe heterocouplings to access the same materials in 3 steps (ca. 30% overall yield). Either enantiomer is accessed at will simply by choosing the order of coupling. A complete comparison of conventional routes to the 25 known molecules in Table versus simple pathways employing reductive Kolbe heterocoupling is graphically illustrated in the SI.