3.2.3. Hydroformylation 2467 3.2.4. Dimerization 2468 3.2.5. Oxidative Cleavage and Ozonolysis 2469 3.2.6. Metathesis 2470 4. Terpenes 2472 4.1. Pinene 2472 4.1.1. Isomerization: R-Pinene 2472 4.1.2. Epoxidation of R-Pinene 2475 4.1.3. Isomerization of R-Pinene Oxide 2477 4.1.4. Hydration of R-Pinene: R-Terpineol 2478 4.1.5. Dehydroisomerization 2479 4.2. Limonene 2480 4.2.1. Isomerization 2480 4.2.2. Epoxidation: Limonene Oxide 2480 4.2.3. Isomerization of Limonene Oxide 2481 4.2.4. Dehydroisomerization of Limonene and Terpenes To Produce Cymene 2481

Chemical Routes for the Transformation of Biomass into Chemicals

In nature, living organisms are constantly producing different macromolecules for their metabolic needs. These macromolecules, such as polysaccharides, polynucleotides, proteins, or polyesters, are essential to organism survival. Their synthesis generally involves in vivo enzyme-catalyzed chaingrowth polymerization reactions of activated monomers, which are generally formed within the cells by complex metabolic processes. Because of their diversity and renewability, microbial polymers such as polysaccharides, bacterial polyhydroxyalkanoates (1) and polyanions such as poly(γ-glutamic acid) (2) have received increasing attention as candidates for industrial applications. In many cases, microorganisms carry out polymer syntheses that are impractical or impossible to accomplish with conventional chemistry. Thus, microbial catalysts enable the production of materials that might otherwise be unavailable. Microbial polymers are synthesized from renewable low-cost feedstocks, and the polymerizations operate under mild process conditions with minimal environmental impact. In addition, microbial polymers provide products that, when disposed, can degrade to nontoxic products.

https://homepages.rpi.edu/~grossr/_doc/publication/Chem.%20Rev.%202001,%20101,%202097-2124.pdf

Polymer Synthesis by In Vitro Enzyme Catalysis

Enzymatic reactions in nonaqueous solvents offer new possibilities for the biotechnological production of many useful chemicals using reactions that are not feasible in aqueous media. In the recent years, the use of enzymes in nonaqueous media has found applications in organic synthesis, chiral synthesis or resolution, modification of fats and oils, synthesis of sugar-based polymers, etc. The use of lipases in esterification reactions to produce industrially important products such as emulsifiers, surfactants, wax esters, chiral molecules, biopolymers, modified fats and oils, structured lipids, and flavor esters is well documented. The interest in using lipases as biotechnological vectors for performing various reactions in both macro- and microaqueous systems has picked up tremendously during the last decade. This review covers important features of lipases and lipase-catalyzed esterification reactions including the kinetics and stability of lipases, and modeling aspects.

Lipases and lipase-catalyzed esterification reactions in nonaqueous media

http://digital.csic.es/bitstream/10261/17327/1/SUCROSE-ESTERS-digitalCSIC.pdf

Enzymatic acylation of di- and trisaccharides with fatty acids: choosing the appropriate enzyme, support and solvent

Biotransformations with Lipases

By complexing glucose and other mono and disaccharides with phenylboronic acid, they were solubilized in many organic solvents. Pseudomonas sp. lipoprotein lipase readily acylated such solubilized sugars in these solvents (no reaction was observed without phenylboronic acid, i.e., when sugars are insoluble in the reaction medium). Solubilized D-glucose was enzymatically acylated with vinyl acrylate on a preparative scale, and the resultant 6-O-acryloylglucose was chemically polymerized to yield a sugar-based polyacrylate with a molecular weight of 14,000 Da.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/bit.260420616

Lipase-catalyzed acyiation of sugars solubilized in hydrophobic solvents by complexation.

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Lipase-catalyzed acyiation of sugars solubilized in hydrophobic solvents by complexation.