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Transfer hydrogenations catalyzed by streptavidin-hosted secondary amine organocatalysts.

ABSTRACT: Here, the streptavidin-biotin technology was applied to enable organocatalytic transfer hydrogenation. By introducing a biotin-tethered pyrrolidine (1) to the tetrameric streptavidin (T-Sav), the resulting hybrid catalyst was able to mediate hydride transfer from dihydro-benzylnicotinamide (BNAH) to α,β-unsaturated aldehydes. Hydrogenation of cinnamaldehyde and some of its aryl-substituted analogues was found to be nearly quantitative. Kinetic measurements revealed that the T-Sav:1 assembly possesses enzyme-like behavior, whereas isotope effect analysis, performed by QM/MM simulations, illustrated that the step of hydride transfer is at least partially rate-limiting. These results have proven the concept that T-Sav can be used to host secondary amine-catalyzed transfer hydrogenations.

SUBMITTER: Santi N

PROVIDER: S-EPMC8330412 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

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Transfer hydrogenations catalyzed by streptavidin-hosted secondary amine organocatalysts.

Santi Nicolò N Morrill Louis C LC Swiderek Katarzyna K Moliner Vicent V Luk Louis Y P LYP

Chemical communications (Cambridge, England) 20210201 15

Here, the streptavidin-biotin technology was applied to enable organocatalytic transfer hydrogenation. By introducing a biotin-tethered pyrrolidine (1) to the tetrameric streptavidin (T-Sav), the resulting hybrid catalyst was able to mediate hydride transfer from dihydro-benzylnicotinamide (BNAH) to α,β-unsaturated aldehydes. Hydrogenation of cinnamaldehyde and some of its aryl-substituted analogues was found to be nearly quantitative. Kinetic measurements revealed that the T-Sav:1 assembly poss ...[more]

PMID: 33496282

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