Commodity chemicals in enantioselective iridium-catalyzed carbonyl allylation

A principal characteristic of a scalable synthetic method is its ability to facilitate the formation of C-C bonds between inexpensive, abundant commodity chemicals without producing stoichiometric metallic byproducts. To this end, a suite of enantioselective iridium-catalyzed reactions for the direct transformation of commodity chemicals to value-added products is described. The reductive couplings discussed herein utilize alcohols as terminal reductants, and therefore do not produce stoichiometric metallic byproducts. The work presented in this dissertation includes 1) a review on couplings of methanol, ethanol, and formaldehyde with π-unsaturated pronucleophiles, and primary research articles describing enantioselective iridium-catalyzed carbonyl allylations involving commodity chemicals 2) allene gas, a petrochemical feedstock, 3) ethanol, a biorenewable C2 feedstock, 4) oxetan-3-one and azetidin-3-ones, abundant building blocks deployed in medicinal chemistry, 5) allyl alcohol, a reliably-sourced acrolein proelectrophile, and its application to the total synthesis of three amphidinolide natural products, and 6) acetyl 1,3-propanediol, a derivative of 1,3-propanediol, as an improved acrolein proelectrophile.