Menaquinone Biosynthesis: The Mechanism of 5,8-Dihydroxy-2-naphthoate Synthase (MqnD). Academic Article

abstract

• MqnD catalyzes the conversion of cyclic dehypoxanthine futalosine (6) to 5,8-dihydroxy-2-naphthoic acid (7) and an uncharacterized product. This study describes a chemoenzymatic synthesis of 6. This synthesis achieved a 2-fold yield enhancement by using titanium(III) citrate as the reducing agent and another 5-fold yield enhancement using a fluorinated analogue of dehypoxanthine futalosine (5) that was converted to 6 by an ipso substitution mechanism. This synthetic route enabled the synthesis of 6 in sufficient quantity to identify the second reaction product and to determine that the MqnD-catalyzed reaction proceeds by a hemiacetal ring opening-tautomerization-retroaldol sequence.

authors

• Begley, Tadhg

published proceedings

• Biochemistry

author list (cited authors)

• Manion-Sommerhalter, H. R., Fedoseyenko, D., Joshi, S., & Begley, T. P.

citation count

• 0

complete list of authors

• Manion-Sommerhalter, Hannah R||Fedoseyenko, Dmytro||Joshi, Sumedh||Begley, Tadhg P

publication date

• June 2021

publisher

• American Chemical Society (ACS)  Publisher

published in

• Biochemistry  Journal

keywords

• Bacillus
• Bacterial Proteins
• Carbon-oxygen Lyases
• Models, Chemical
• Nucleosides
• Vitamin K 2

PubMed Central ID

• 34143602

Digital Object Identifier (DOI)

• 10.1021/acs.biochem.1c00257

start page

• 1947

end page

• 1951

volume

• 60

issue

• 25

URL

• http://dx.doi.org/10.1021/acs.biochem.1c00257