Alkenyl phenols are utilized by nature in the construction of one of the most important biopolymers, lignin. Using similar building blocks, an array of distinct structures can be formed by selective dimerization of the starting phenols to form lignans, neolignans, oxyneolignans, and norlignans. Given the multitude of possible outcomes, many methods have been reported to affect the desired bond formations and access these biologically relevant scaffolds. The most biomimetic of these methods, discussed here, involve the unprotected phenols undergoing oxidative bond formation that proceeds via dehydrogenative coupling. This review aims to place the known literature in context, highlight the progress made toward the synthesis of these important molecules, and recognize the gaps and limitations that still exist.