Enantioselective “Clip-Cycle” Synthesis of Di-, Tri- and Spiro- Substituted Tetrahydropyrans

ω-Unsaturated alcohols were “clipped” via alkene metathesis to a thioester activating group, which was followed by a chiral phosphoric acid catalyzed intramolecular oxa-Michael cyclization to yield tetrahydropyrans and spiro-tetrahydropyrans with...

Efficient whole-cell oxidation of α,β-unsaturated alcohols to α,β-unsaturated aldehydes through the cascade biocatalysis of alcohol dehydrogenase, NADPH oxidase and hemoglobin

Background α,β-Unsaturated aldehydes are widely used in the organic synthesis of fine chemicals for application in products such as flavoring agents, fragrances and pharmaceuticals. In the selective oxidation of α,β-unsaturated alcohols to the corresponding α,β-unsaturated aldehydes, it remains challenging to overcome poor selectivity, overoxidation and a low atom efficiency in chemical routes. Results An E. coli strain coexpressing the NADP+-specific alcohol dehydrogenase YsADH and the oxygen-dependent NADPH oxidase TkNOX was constructed; these components enabled the NADP+ regeneration and catalyzed the oxidation of 100 mM 3-methyl-2-buten-1-ol to 3-methyl-2-butenal with a yield of 21.3%. The oxygen supply was strengthened by introducing the hemoglobin protein VsHGB into recombinant E. coli cells and replacing the atmosphere of the reactor with pure oxygen, which increased the yield to 51.3%. To further improve catalytic performance, the E. coli cells expressing the multifunctional fusion enzyme YsADH-(GSG)-TkNOX-(GSG)-VsHGB were generated, which completely converted 250 mM 3-methyl-2-buten-1-ol to 3-methyl-2-butenal after 8 h of whole-cell oxidation. The reaction conditions for the cascade biocatalysis were optimized, in which supplementation with 0.2 mM FAD and 0.4 mM NADP+ was essential for maintaining high catalytic activity. Finally, the established whole-cell system could serve as a platform for the synthesis of valuable α,β-unsaturated aldehydes through the selective oxidation of various α,β-unsaturated alcohols. Conclusions The construction of a strain expressing the fusion enzyme YsADH-(GSG)-TkNOX-(GSG)-VsHGB achieved efficient NADP+ regeneration and the selective oxidation of various α,β-unsaturated alcohols to the corresponding α,β-unsaturated aldehydes. Among the available redox enzymes, the fusion enzyme YsADH-(GSG)-TkNOX-(GSG)-VsHGB has become the most recent successful example to improve catalytic performance in comparison with its separate components.

Efficient whole-cell oxidation of α,β-unsaturated alcohols to α,β-unsaturated aldehydes through the cascade biocatalysis of alcohol dehydrogenase, NADPH oxidase and hemoglobin

Background: α,β-Unsaturated aldehydes are widely used in the organic synthesis of fine chemicals for application in products such as flavoring agents, fragrances and pharmaceuticals. In the selective oxidation of α,β-unsaturated alcohols to the corresponding α,β-unsaturated aldehydes, it remains challenging to overcome poor selectivity, overoxidation and a low atom efficiency in chemical routes. Results: An E. coli strain coexpressing the NADP+-specific alcohol dehydrogenase YsADH and the oxygen-dependent NADPH oxidase TkNOX was constructed; these components enabled the NADP+ regeneration and catalyzed the oxidation of 100 mM 3-methyl-2-buten-1-ol to 3-methyl-2-butenal with a yield of 21.3%. The oxygen supply was strengthened by introducing the hemoglobin protein VsHGB into recombinant E. coli cells and replacing the atmosphere of the reactor with pure oxygen, which increased the yield to 51.3%. To further improve catalytic performance, the E. coli cells expressing the multifunctional fusion enzyme YsADH-(GSG)-TkNOX-(GSG)-VsHGB were generated, which completely converted 250 mM 3-methyl-2-buten-1-ol to 3-methyl-2-butenal after 8 h of whole-cell oxidation. The reaction conditions for the cascade biocatalysis were optimized, in which supplementation with 0.2 mM FAD and 0.4 mM NADP+ was essential for maintaining high catalytic activity. Finally, the established whole-cell system could serve as a platform for the synthesis of valuable α,β-unsaturated aldehydes through the selective oxidation of various α,β-unsaturated alcohols. Conclusions: The construction of a strain expressing the fusion enzyme YsADH-(GSG)-TkNOX-(GSG)-VsHGB achieved efficient NADP+ regeneration and the selective oxidation of various α,β-unsaturated alcohols to the corresponding α,β-unsaturated aldehydes. Among the available redox enzymes, the fusion enzyme YsADH-(GSG)-TkNOX-(GSG)-VsHGB has become the most recent successful example to improve catalytic performance in comparison with its separate components.

Dehydration of Biomass-Derived Butanediols over Rare Earth Zirconate Catalysts

The aim of this work is to develop an effective catalyst for the conversion of butanediols, which is derivable from biomass, to valuable chemicals such as unsaturated alcohols. The dehydration of 1,4-, 1,3-, and 2,3-butanediol to form unsaturated alcohols such as 3-buten-1-ol, 2-buten-1-ol, and 3-buten-2-ol was studied in a vapor-phase flow reactor over sixteen rare earth zirconate catalysts at 325 °C. Rare earth zirconates with high crystallinity and high specific surface area were prepared in a hydrothermal treatment of co-precipitated hydroxide. Zirconates with heavy rare earth metals, especially Y2Zr2O7 with an oxygen-defected fluorite structure, showed high catalytic performance of selective dehydration of 1,4-butanediol to 3-buten-1-ol and also of 1,3-butanediol to form 3-buten-2-ol and 2-buten-1-ol, while the zirconate catalysts were less active in the dehydration of 2,3-butanediol. The calcination of Y2Zr2O7 significantly affected the catalytic activity of the dehydration of 1,4-butanediol: a calcination temperature of Y2Zr2O7 at 900 °C or higher was efficient for selective formation of unsaturated alcohols. Y2Zr2O7 with high crystallinity exhibits the highest productivity of 3-buten-1-ol from 1,4-butanediol at 325 °C.

Efficient whole-cell oxidation of α,β-unsaturated alcohols to α,β-unsaturated aldehydes through cascade biocatalysis of alcohol dehydrogenase, NADPH oxidase and hemoglobin

Background: α,β-unsaturated aldehydes are widely used in as organic synthesis of fine chemicals such as flavor, fragrances and pharmaceuticals. The selective oxidation of α,β-unsaturated alcohols to the corresponding α,β-unsaturated aldehydes remains challenging to overcome poor selectivity, over-oxidation and low atom efficiency in chemical routes. Results: An E. coli strain co-expressing NADP+-specific alcohol dehydrogenase YsADH and oxygen-dependent NADPH oxidase TkNOX was constructed, which enabled the NADP+ regeneration and catalyzed the oxidation of 100 mM 3-methyl-2-buten-1-ol to 3-methyl-2-butenal with the yield of 21.3%. The oxygen supply was strengthened by introducing the hemoglobin VsHGB into recombinant E. coli cells and replacing the atmosphere of the reactor with pure oxygen, which increased the yield up to 51.3%. To further improve catalytic performance, the E. coli cells expressing the multifunctional fusion enzyme YsADH-(GSG)-TkNOX-(GSG)-VsHGB were achieved, which totally converted 250 mM 3-methyl-2-buten-1-ol to 3-methyl-2-butenal after 8 h of whole-cell oxidation. The reaction conditions of the cascade biocatalysis were optimized, in which the supplement of 0.2 mM FAD and 0.4 mM NADP+ was essential for maintaining high catalytic activity. Finally, the established whole-cell system could serve as a platform for the synthesis of valuable α,β-unsaturated aldehydes from selective oxidation of various α,β-unsaturated aldehydes. Conclusions: The construction of the strain expressing the fusion enzyme YsADH-(GSG)-TkNOX-(GSG)-VsHGB fulfilled efficient NADP+ regeneration and selective oxidation of various α,β-unsaturated alcohols to the corresponding α,β-unsaturated aldehydes. With the scope of redox enzymes, the fusion enzyme YsADH-(GSG)-TkNOX-(GSG)-VsHGB has become the latest successful example to improve catalytic performance in comparison with separated counterparts.