Compartmentalization in Biocatalysis

Chemoenzymatic Cascades Combining Biocatalysis and Transition Metal Catalysis for Asymmetric Synthesis

“…Therefore, chemists have envisaged different solutions if a concurrent chemoenzymatic transformation cannot be done due to catalyst(s), auxiliary reagent(s) or reaction conditions incompatibilities. In some cases, the use of a compartmentalized system (resembling what occurs in living cells), by segregating the reactions which are incompatible in different compartments, has largely improved the outcome of the cascade process [77] …”

“…the Pd‐mediated Buchwald–Hartwig amination of chiral amines obtained after ATA‐catalyzed biotransamination, [26] or in enzymatic halocyclizations using a haloperoxidase combined with a Pd‐catalyzed Suzuki‐type cross coupling [78] . However, the interactions among the different species are not completely avoided in the reaction medium, and can be problematic when isolating the final products [77] …”

“…In some cases, the use of a compartmentalized system (resembling what occurs in living cells), by segregating the reactions which are incompatible in different compartments, has largely improved the outcome of the cascade process. [77] Since enzymatic transformations occur in water while metal catalysis usually works in organic media, at first sight the use of biphasic systems adding an immiscible solvent could be envisaged as a solution. In fact, it has been successfully applied in, e.g.…”

“…[78] However, the interactions among the different species are not completely avoided in the reaction medium, and can be problematic when isolating the final products. [77] Another way to physically separate different components is using polydimethylsiloxane (PDMS) thimbles as described by Gröger and co-workers in the combination of Wacker-Tsuji oxidation and enzymatic steps. To overcome the enzymatic inhibition observed due to the Cu salt used as co-oxidant, the compartmentalization of both reactions was developed, achieving first the Wacker-Tsuji oxidation inside the thimble, and then, LkADH, the cofactor and the buffer were added in the outer part.…”

Recyclable and Scalable Chemoenzymatic Dynamic Kinetic Resolution of Secondary Alcohols Using Rotating Bed Reactors for Catalyst Compartmentalization

“…Novel reaction designs of lipase-metal DKR of secondary alcohols are still needed to meet the demand for more robust methods with readily available and safer catalysts. For example, compartmentalizing the catalysts is a promising option to overcome incompatibility issues and facilitate operational processes. , Inspired by nature’s elegant biological compartments, catalyst compartmentalization involves the organization or segregation of catalysts into distinct physical structures (compartments), aiming to improve the efficiency and selectivity of the reactions. , …”