Back to Search Start Over

Enantioselective Enzymatic Naphthoyl Ring Reduction.

Authors :
Willistein, Max
Haas, Julian
Fuchs, Jonathan
Estelmann, Sebastian
Ferlaino, Sascha
Müller, Michael
Lüdeke, Steffen
Boll, Matthias
Source :
Chemistry - A European Journal. 8/27/2018, Vol. 24 Issue 48, p12505-12508. 4p.
Publication Year :
2018

Abstract

Abstract: Birch reductions of aromatic hydrocarbons by means of single‐electron‐transfer steps depend on alkali metals, ammonia, and cryogenic reaction conditions. In contrast, 2‐naphthoyl‐coenzyme A (2‐NCoA) and 5,6‐dihydro‐2‐NCoA (5,6‐DHNCoA) reductases catalyze two two‐electron reductions of the naphthoyl‐ring system to tetrahydronaphthoyl‐CoA at ambient temperature. Using a number of substrate analogues, we provide evidence for a Meisenheimer complex‐analogous intermediate during 2‐NCoA reduction, whereas the subsequent reduction of 5,6‐dihydro‐2‐NCoA is suggested to proceed via an unprecedented cationic transition state. Using vibrational circular dichroism (VCD) spectroscopy, we demonstrate that both enzymatic reductions are highly stereoselective in D2O, providing an enantioselective pathway to products inaccessible by Birch reduction. Moreover, we demonstrate the power of VCD spectroscopy to determine the absolute configuration of isotopically engendered alicyclic stereocenters. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
09476539
Volume :
24
Issue :
48
Database :
Academic Search Index
Journal :
Chemistry - A European Journal
Publication Type :
Academic Journal
Accession number :
131481164
Full Text :
https://doi.org/10.1002/chem.201802683