Enzymatic and chemo-enzymatic strategies to produce highly valuable chiral amines from biomass with ω-transaminases on 2D zeolites

Abstract

Amino transaminases (ATAS) have been supported on a 2D ITQ-2 zeolite through electrostatic interactions, resulting in highly stable an active biocatalyst to obtain a variety of valuable chiral amines starting from prochiral ketones derived from biomass. We have extended the biocatalyst applications by designing a chemo-enzymatic process that allows to obtain as first step prochiral ketones from biomass derived compounds, through an aldol condensation-reduction step using a bifunctional metal/base catalyst. The prochiral ketone is subsequently converted in the chiral amine using the immobilized ATA. We show that it is feasible to couple both steps in a semi-continuous process to produce industrially relevant chiral amines with yields > 95% and ∼100% ee.

Bimetallic Sites for Catalysis: From Binuclear Metal Sites to Bimetallic Nanoclusters and Nanoparticles

“…Owing to the advances in the synthetic modification of enzymes, the synthesis of enzyme mimicking molecules, and genetic modification of cells to produce new enzymes, will open more opportunities for manufacturing chemicals from biomass. No doubt that enzymatic and chemo-enzymatic processes will add more potential to the catalysis field, and the combination of enzymes and solid catalysts to form hybrid systems will enable novel catalytic transformations which are not feasible via conventional routes. − As always, we expect major advances within the interphase of the different confluent fields and this progress will bring new insights and inspirations to future developments of catalysis science and technology.…”

Advances in One-Pot Chiral Amine Synthesis Enabled by Amine Transaminase Cascades: Pushing the Boundaries of Complexity

“…Lately, ATAs have been immobilized on ITQ-2 zeolite and combined with a bifunctional base–metal catalyst formed by Pd nanoparticles supported on MgO, resulting in a one-pot chemoenzymatic cascade chiral amine synthesis starting from prochiral ketones derived from biomass (Scheme ). The process results in yields of >95% and ∼100% ee …”

“…63 Lately, ATAs have been immobilized on ITQ-2 zeolite and combined with a bifunctional base−metal catalyst formed by Pd nanoparticles supported on MgO, resulting in a one-pot chemoenzymatic cascade chiral amine synthesis starting from prochiral ketones derived from biomass (Scheme 19). 64 The process results in yields of >95% and ∼100% ee. 64 Recently, a chemoenzymatic one-pot procedure was developed for the synthesis of the key chiral intermediate of pralsetinib in an aqueous medium (Schemes 20 and 29).…”

“…64 The process results in yields of >95% and ∼100% ee. 64 Recently, a chemoenzymatic one-pot procedure was developed for the synthesis of the key chiral intermediate of pralsetinib in an aqueous medium (Schemes 20 and 29). 65 This green synthesis consists of a base-catalyzed C-alkylation in an aqueous CTAB solution in combination with ATAs in an aqueous media and achieved yields exceeding 80% with >99% ee (Scheme 20).…”

Continuous flow-mode synthesis of (chiral) amines with transaminase: a strategic biocatalytic approach to essential building blocks

“…Fig.39Schematic representation of the chemo-enzymatic process involving a flow asymmetric synthesis of S-4-(4-methoxyphenyl)-2butanamine (framed compound), described by Corma et al232 The dotted area represents the semi-continuous batch reactor hosting the chemocatalytic step of the cascade (aldol-reduction).…”