Strategic enzymatic enantioselective desymmetrization of prochiral cyclohexa-2,5-dienones.

Autor: Kattula B; Department of Applied Biology, Hyderabad, India. anthony@csiriict.in.; Academy of Scientific and Innovative Research (AcSIR), Ghaziabad-201002, India., Munakala A; Department of Organic Synthesis and Process Chemistry, Hyderabad, Telangana, India. rchegondi@iict.res.in., Kashyap R; Department of Applied Biology, Hyderabad, India. anthony@csiriict.in., Nallamilli T; Department of Organic Synthesis and Process Chemistry, Hyderabad, Telangana, India. rchegondi@iict.res.in.; Academy of Scientific and Innovative Research (AcSIR), Ghaziabad-201002, India., Nagendla NK; Department of Analytical and Structural Chemistry, CSIR-Indian Institute of Chemical Technology, Hyderabad-500 007, Telangana, India.; Academy of Scientific and Innovative Research (AcSIR), Ghaziabad-201002, India., Naza S; Department of Applied Biology, Hyderabad, India. anthony@csiriict.in.; Academy of Scientific and Innovative Research (AcSIR), Ghaziabad-201002, India., Mudiam MKR; Department of Analytical and Structural Chemistry, CSIR-Indian Institute of Chemical Technology, Hyderabad-500 007, Telangana, India.; Academy of Scientific and Innovative Research (AcSIR), Ghaziabad-201002, India., Chegondi R; Department of Organic Synthesis and Process Chemistry, Hyderabad, Telangana, India. rchegondi@iict.res.in.; Academy of Scientific and Innovative Research (AcSIR), Ghaziabad-201002, India., Addlagatta A; Department of Applied Biology, Hyderabad, India. anthony@csiriict.in.; Academy of Scientific and Innovative Research (AcSIR), Ghaziabad-201002, India.
Jazyk: angličtina
Zdroj: Chemical communications (Cambridge, England) [Chem Commun (Camb)] 2024 Jun 25; Vol. 60 (52), pp. 6647-6650. Date of Electronic Publication: 2024 Jun 25.
DOI: 10.1039/d4cc02181a
Abstrakt: Asymmetric desymmetrization through the selective reduction of one double bond of prochiral 2,5-cyclohexadienones is highly challenging. A novel method has been developed for synthesizing chiral cyclohexenones by employing an ene-reductase ( Bacillus subtilis YqjM) enzyme that belongs to the OYE family. Our strategy demonstrates high substrate scope and enantioselectivity towards substrates containing all-carbon as well as heteroatom ( O , N )-containing quaternary centers. The mechanistic studies ( k H/D = ∼1.8) indicate that hydride transfer is probably the rate-limiting step. Mutation of several active site residues did not affect the stereochemical outcomes. This work provides a convenient way of synthesizing various enantioselective γ,γ-disubstituted cyclohexanones using enzymes.
Databáze: MEDLINE
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