Many of the substrates in Table are high-value building blocks that can now be accessed in much simpler or considerably different ways. In fact, these substrates serve as yet another demonstration of how labor intensive 2e --based approaches can be replaced with routes arising from radical retrosynthesis logic. For instance, dimethyl adipate 8, an important precursor for adipic acid, can be prepared from biomass-derived material via 4-step functional group manipulations involving hydroformylation with precious metal catalysis. In contrast, the rAP-Kolbe reaction afforded 8 in a single step from monomethyl succinate, which could also derived from bio-based succinic acid. The diamine parent of 11 is a valuable building block for polyamide 1010 and is currently prepared from sebacic acid after three functional group manipulation steps. In contrast, rAP-Kolbe reaction opens a new avenue to access this compound from ε-caprolactam, a commodity chemical (ca. $3/kg), through efficient C-C bond formation. Diol 12 is an essential building block for a promising degradable Acetone/toluene = 30/1 was used as solvent. d 5 equiv. of the coupling acid was used. e 6 equiv. of the coupling acid was used. f 3 equiv. of the coupling acid was used. g Price of free amino acid. (C) Current limitations. $5000/g (Aurora Fine) g $5000/g (Aurora Fine) g Bio-derived surrogate of polyethylene, yet it is currently synthesized via hazardous LAH reduction of the corresponding diacid. In contrast, 10-hydroxydecanoic acid (derived from castor oil) can be converted to 12 in 84% isolated yield under rAP without any protection of the terminal alcohol. Diketone 13, a potentially useful building block ($3000/g), can be easily derived from levulinic acid, one of the top-12 platform chemicals that can be mass produced from biorefineries according to the US Department of Energy. Compounds 15 and 16, now easily available using rAP, represent a new derivatization method of hydrocinnamic acid derivatives, bio-based aromatic acids available from lignin. Amino acid (AA) dimer 17 (currently sold for ca. $5000/g) is known to be an important intermediate for a potent allosteric inhibitor and has been previously synthesized in 7 steps as a racemate, whereas rAP dimerization of protected aspartate delivers it as a single diastereomer in 86% isolated yield. Similarly, dimeric AA 18, a known carbon-isostere of disulfide linkages in peptides, can be easily accessed through glutamate dimerization. Past approaches to structures like these are low-yielding Kolbe reaction or olefin metathesis from unnatural amino acids. Finally, bis-azetidine 19 ($1600 for 250 mg, HCl salt), a useful piperazine isostere in medicinal chemistry, is an example of a workable secondary coupling.