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Chemical Structure| 15086-94-9 Chemical Structure| 15086-94-9
Chemical Structure| 15086-94-9

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Synonyms: Acid Red 87 free base

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Lu, Yen-Chu ; Adukure, Ronald D ; Roy, Satyajit ; Chien, Derek L ; McGill, Matthew J ; Polara, Sarthi , et al.

Abstract: Hydrogen atom transfer (HAT) constitutes a powerful mechanism exploited in biology and chemistry to functionalize ubiquitous C(sp3)−H bonds in organic molecules. Despite its synthetic potential, achieving stereocontrol in chemical HAT-mediated C−H functionalization transformations remains challenging. By merging the radical reactivity of thiamine (ThDP)-dependent enzymes with chemical hydrogen atom transfer, we report here a photobiocatalytic strategy for the enantioselective C(sp3)−H acylation of an organic substrate, a transformation not found in nature nor currently attainable by chemical means. This method enables the direct functionalization of benzylic C(sp3)−H sites in a broad range of substrates to furnish valuable enantioenriched ketone motifs with good to high enantioselectivity (up to 96% ee). Mechanistic and spectroscopic studies support the involvement of radical species derived from the Breslow intermediate and C−H substrate, highlight the critical role of the photocatalyst and hydrogen atom abstraction reagents for productive catalysis, and reveal a specific enzyme/photocatalyst interaction favoring single electron transfer during catalysis. Further insights into how the enantioselectivity of the C−C bond-forming reaction is controlled by the enzyme and influenced by active site mutations were gained via molecular modeling. This study illustrates the productive integration of ThDP-mediated biocatalysis with chemical HAT, expanding the range of asymmetric C(sp3)−H functionalization transformations that can be accessed through biocatalysis.

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Product Details of Eosin Y

CAS No. :15086-94-9
Formula : C20H8Br4O5
M.W : 647.89
SMILES Code : O=C1OC2(C3=C(OC4=C2C=C(Br)C(O)=C4Br)C(Br)=C(O)C(Br)=C3)C5=C1C=CC=C5
Synonyms :
Acid Red 87 free base
MDL No. :MFCD00036189
InChI Key :DBZJJPROPLPMSN-UHFFFAOYSA-N
Pubchem ID :27020

Safety of Eosin Y

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302
Precautionary Statements:P280-P305+P351+P338
 

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