Greening the Synthesis of Biorenewable Fuels and Chemicals by Stoichiometric Reagentless Organic Transformations

Abstract

Reagentless organic synthesis (ROS) can be envisaged as a corollary of the principles of green chemistry, wherein the reactant molecules undergo chemical transformations under the influence of heat, light, sound, or electricity and afford the desired product without necessitating stoichiometric reagents. The predominantly catalytic processes ensure excellent atom economy and minimize waste formation, making the synthetic strategies inherently green. However, since most starting materials stem from exhaustible resources like petroleum, the processes are not entirely sustainable. Reagents and reactants are often used interchangeably, but utmost care should be taken to minimize or eliminate the use of any chemical or material in a chemical transformation that does not appear in a balanced chemical equation. The ideal disposition would be the reagentless synthesis of chemicals using renewable starting materials. In this regard, biomass is a renewable carbon source with the commercial potential to supplant petroleum in producing fuels, chemicals, and polymers. Even though many chemocatalytic biomass value addition processes can be contemplated as ROS, they are somewhat scattered in the literature and have never been deliberated coherently from this perspective. Integration of ROS with biorenewable starting materials can ensure the much-anticipated all-round sustainability of the organic chemical industry. This unique review discusses the merits of synthesizing fuels and chemicals from biomass components following reagentless synthetic steps, critically analyzes the literature data, identifies the research gaps, and proposes future directives. © 2022 American Chemical Society.