Promiscuity of Lipase‐Catalyzed Reactions for Organic Synthesis: A Recent Update

Abstract

Lipase-catalyzed organic reactions have widely been practiced in the past three decades. In addition to its wide acceptance in conventional reactions such as hydrolysis, transesterification, and enantiopure synthesis (kinetic resolution and dynamic kinetic resolution) several reports on the catalytic promiscuity of lipases have also been published. The concept of promiscuity, where lipase catalyzes reactions beyond its natural function, has been perceived as a useful phenomenon which can enhance the utility of lipase as a biocatalyst. Many useful organic reactions such as Aldol condensation, Hantzsch reaction, Canizzaro reaction, Mannich reaction, Baylis-Hillman reaction, Knoevenagel condensation, Michael addition, Ugi reaction, and oxidation catalyzed by lipases have surfaced in the literature. The current review is a critical compilation of such research findings to put forth the synthetic applications of lipase, beyond the orthodox biocatalytic toolbox.

Novozym 435: the “perfect” lipase immobilized biocatalyst?

“…Thus, lipases are used in vitro to catalyze reactions different from those of the natural hydrolase function, [49][50][51][52][53][54] such as esterification, [55][56][57][58][59][60][61] acidolysis, [62][63][64][65][66][67] interesterificaton, [68][69][70][71] transesterification, [72][73][74][75][76] aminolysis, [77][78][79][80][81] perhydrolysis, 82,83 etc., together with a collection of the so-called promiscuous reactions. [84][85][86][87][88][89][90][91][92] Lipases are usually quite stable, and so they have been used in diverse media, like aqueous media, organic solvents, [93][94][95] ionic liquids, [96]…”

The Hitchhiker's guide to biocatalysis: recent advances in the use of enzymes in organic synthesis

“…A number of hydrolases, such as lipases, have been demonstrated to catalyse a wide range of reactions that do not occur in vivo. 230,231 7.2.1 Addition reactions. Enzymatic Michael addition reactions, catalysed by a variety of hydrolases, have been widely reported with N and S nucleophiles.…”

Novel Methodologies for Chemical Activation in Organic Synthesis under Solvent-Free Reaction Conditions

“…Due to their high efficiency and versatility, enzymes (in particular lipases) have been used both in small-scale settings (e.g., laboratories) and large-scale synthetic industrial pharmaceutical processes for the preparation of a wide variety of organic compounds. The necessary synthetic steps that may be assigned to enzymes can involve hydrolytic, enantioselective, condensation reactions, and even multicomponent reactions [ 97 , 98 , 99 , 100 ]. These processes can be carried out on scales of several grams in either batch or continuous flow reactors [ 101 ].…”