Development and applications of selective hydroesterification reactions

Transition-metal-catalyzed hydroesterification is an atom-efficient process to produce esters from unsaturated bonds, alcohols, and CO that is seeing significantly increased utility. Careful choice of ligand has a strong influence on the selectivity, efficiency, and stability of the catalyst. While simple alkenes and alkynes have historically been studied for hydroesterification, recent advances have enabled selective hydroesterification of more complex structures. CO replacements have been developed to avoid the acute toxicity of CO and the frequent need for high-pressure reactors. The catalyzed addition of carbon monoxide to unsaturated compounds has drawn considerable attention over the past decade where more structurally complex molecules are made with high selectivities. In this review, we highlight some of the recent contributions that have significantly broadened the scope for the selective hydroesterification of alkenes and alkynes with alcohols to give esters. Key mechanistic features that drive linear or branched selectivity and how proper ligand choice plays an essential role are discussed. As a result, the utility for hydroesterification has expanded to new applications, which have also been highlighted. The catalyzed addition of carbon monoxide to unsaturated compounds has drawn considerable attention over the past decade where more structurally complex molecules are made with high selectivities. In this review, we highlight some of the recent contributions that have significantly broadened the scope for the selective hydroesterification of alkenes and alkynes with alcohols to give esters. Key mechanistic features that drive linear or branched selectivity and how proper ligand choice plays an essential role are discussed. As a result, the utility for hydroesterification has expanded to new applications, which have also been highlighted. a substitution reaction where the nucleophile is an alcohol (typically the solvent). a reaction to incorporate carbon monoxide into organic and inorganic substrates. a mixture of >30 compounds obtained from the dimerization of 1-butene and 2-butene. a catalytic reaction in which at least two consecutive reactions occur such that each subsequent reaction occurs only in the presence of the chemical functionality formed in the previous step. an organic compound that contains both an alkene and an alkyne functionality. a carbonylation reaction to incorporate carbon monoxide and an alcohol into unsaturated organic compounds (alkenes, alkynes) to form an ester. a carbonylation reaction to incorporate carbon monoxide and H2 into unsaturated organic compounds to form an aldehyde. a reaction where one chemical entity interposes itself into an existing bond. the change in the rate of a reaction when an atom (often hydrogen) is replaced by one of its isotopes (often deuterium). a type of alkene containing both an electron-withdrawing and an electron-donating substituent. an industrial mixture of olefins comprising 26% 1-butene, 17% 2-butene, 42% isobutylene, 0.3% 1,3-butadiene, and 15% butanes. the slowest step in a chemical reaction that determines the speed at which the overall reaction proceeds. the preference for a reaction to form one product over another. turnover per unit time. the number of moles of substrate that a mole of catalyst can convert before becoming inactivated.