Promiscuous Candida antarctica lipase B-catalyzed synthesis of β-amino esters via aza-Michael addition of amines to acrylates

Dhake, Kishor P.; Tambade, Pawan J.; Singhal, Rekha S.; Bhanage, Bhalchandra M.

doi:10.1016/j.tetlet.2010.06.089

Cited by 53 publications

(39 citation statements)

References 37 publications

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“…Subsequently, other hydrolase-catalyzed Michael addition reactions were reported. In 2010, Bhanage et al developed an efficient protocol for the regioselective aza-Michael addition of amines with acrylates using Candida antarctica lipase B (CALB) as a biocatalyst at 60°C ( Figure 3) [19]. The universality of the reaction, including the reactions of various primary and secondary amines with different acrylates, was also studied.…”

Section: Carbon-heteroatom Bond Formation Michael Additionmentioning

confidence: 99%

Hydrolase-Catalyzed Promiscuous Reactions and Applications in Organic Synthesis

Wang¹,

Wang²

2021

Molecular Biotechnology

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The potential of biocatalysis becomes increasingly recognized as an efficient and green tool for modern organic synthesis. Biocatalytic promiscuity, a new frontier extended the use of enzymes in organic synthesis, has attracted much attention and expanded rapidly in the past decade. It focuses on the enzyme catalytic activities with unnatural substrates and alternative chemical transformations. Exploiting enzyme catalytic unconventional reactions might lead to improvements in existing catalysts and provide novel synthesis pathways that are currently not available. Among these enzymes, hydrolase (such as lipase, protease, acylase) undoubtedly has received special attention since they display remarkable activities for some unexpected reactions such as aldol reaction and other novel carbon-carbon and carbon-heteroatom bond-forming reactions. This chapter introduces the recent progress in hydrolase catalytic unconventional reactions and application in organic synthesis. Some important examples of hydrolase catalytic unconventional reactions in addition reactions are reviewed, highlighting the catalytic promiscuity of hydrolases focuses on aldol reaction, Michael addition, and multicomponent reactions.

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Section: Carbon-heteroatom Bond Formation Michael Additionmentioning

confidence: 99%

Hydrolase-Catalyzed Promiscuous Reactions and Applications in Organic Synthesis

Wang¹,

Wang²

2021

Molecular Biotechnology

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“…These β-amino carbonyl compounds are versatile intermediates for the synthesis of a variety of biologically important natural products and antibiotics, and are also useful in fine chemicals and pharmaceuticals. [42,43] Therefore, the reactions of PILs with α,β unsaturated esters methyl methacrylate (15) and butyl acrylate (16) were designed, which were studied under the same previously used conditions (50-60°C, 24 h). For non-polar reactants, the presence of free nitric acid was required to attain good product yields, and the acidity of free acetic acid was not strong enough to drive the acid catalysis.…”

Section: Reactive Behaviours Of Pils With Polar Reactantsmentioning

confidence: 99%

Understanding the Role of Protic Ionic Liquids (PILs) in Reactive Systems: Rational Selection of PILs for the Design of Green Synthesis Strategies for Allylic Amines and β‐Amino Esters

et al. 2019

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The reactive behaviour of protic ionic liquids (PILs) has been shown to be governed not only by their chemical structures but also by their global compositions, which include the presence of free acids and bases at equilibrium with ionic pairs. Six PILs composed of primary, secondary, or tertiary alkyl ammonium cations with two couterions, nitrate or acetate, were tested in model reactions with unsaturated substrates. The free species that were naturally present in these liquids were identified by cyclic voltammetry. Only tributylammonium nitrate was found to be mostly composed just of the ionic pair; the other five PILs also contain variable amounts of free acid and amine. In reactive systems, these free species determine the products of the reaction. In particular, allylic amines and β‐amino esters were obtained in good yields (91 and 75 %, respectively) by reaction of conjugated dienes and acrylates in the presence of PILs. By taking into account the actual composition of each PIL, it was possible to direct the reaction path towards a specific product with good yields, to ensure acid catalysis, to avoid polymerization of the substrate, and to promote phase transfer of products. These results establish some useful guidelines for the rational design of new PIL‐based one‐step synthetic strategies.

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“…The reaction between methyl acrylate and secondary amines such as diethylamine, pyrrolidine and piperidine has been efficiently accelerated by BLAP immobilized as cross‐linked aggregates . Similarly, CAL‐B proved to be an effective enzyme for the regioselective aza‐Michael reaction of primary and secondary amines with alkyl acrylates, forming the corresponding β‐amino esters in 31–94% yield after a short reaction time at 60°C in toluene (Scheme ) . Recently, Castillo and co‐workers have developed a solvent engineering strategy to control the chemoselectivity of the CAL‐B‐catalyzed aza‐Michael addition between benzylamine and various α,β‐unsaturated alkyl and phenylacrylate esters, and were able to explain the formation of aza‐Michael adducts or aminolysis products by taking into account thermodynamic interactions .…”

Section: Carbon–heteroatom Bond‐formation Reactionsmentioning

confidence: 99%

Recent Advances in Biocatalytic Promiscuity: Hydrolase‐Catalyzed Reactions for Nonconventional Transformations

López-Iglesias

Gotor‐Fernández

2015

The Chemical Record

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Enzymes has emerged in recent decades as ideal catalysts for synthetic transformations in mild reaction conditions. Their capacity to accelerate a myriad of biotransformations with high levels of selectivity and broad substrate specificity including excellent atom economy has led to a current full recognition. The six classes of enzymes (oxidoreductases, transferases, hydrolases, lyases, isomerases and ligases) possess outstanding abilities to perform specific modifications in target molecules. Nevertheless, in the last fifteen years, novel examples have appeared related to nonconventional processes catalyzed by various classes of biocatalysts. Amongst these, hydrolases have received special attention since they display remarkable activities in initially unexpected reactions such as carbon-carbon and carbon-heteroatom bond formation reactions, oxidative processes and novel hydrolytic transformations. In this review, the main findings in this area will be disclosed, highlighting the catalytic properties of hydrolases not only to catalyze single processes but also multicomponent and tandem nonconventional reactions.

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Promiscuous Candida antarctica lipase B-catalyzed synthesis of β-amino esters via aza-Michael addition of amines to acrylates

Cited by 53 publications

References 37 publications

Hydrolase-Catalyzed Promiscuous Reactions and Applications in Organic Synthesis

Hydrolase-Catalyzed Promiscuous Reactions and Applications in Organic Synthesis

Understanding the Role of Protic Ionic Liquids (PILs) in Reactive Systems: Rational Selection of PILs for the Design of Green Synthesis Strategies for Allylic Amines and β‐Amino Esters

Recent Advances in Biocatalytic Promiscuity: Hydrolase‐Catalyzed Reactions for Nonconventional Transformations

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