Furukawa Natsuko, Chen Xuejie, Asano Satoshi, Matsumoto Marina, Wu Yuxin, Murata Kohei, Takeuchi Atsuko, Tode Chisato, Tie Jian-Ke, Hirota Yoshihisa, Suhara Yoshitomo
Laboratory of Organic Synthesis and Medicinal Chemistry, Department of Bioscience and Engineering, College of Systems Engineering and Science, Shibaura Institute of Technology, 307 Fukasaku, Minuma-ku, Saitama 337-8570, Japan.
Department of Biology, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, USA.
J Mol Struct. 2023 Mar 15;1276. doi: 10.1016/j.molstruc.2022.134614. Epub 2022 Nov 24.
Prior to being utilized in the body, dietary vitamin K homologues are converted to menaquinone-4 (MK-4) by cleavage of the side chain part followed by prenylation. We predicted that the prenylation would occur due to the electron deficiency at the C-1' position of the allyl moiety. Therefore, as an alternative method to make the C-1' position electron-deficient, a new vitamin K derivative was synthesized by introducing a ketone group, and its conversion to MK-4 was investigated. Introduction of a ketone group at the C-1' position of the side chain of 2',3'-dihydrophylloquinone, which is known to resist conversion to MK-4, induced conversion to the MK-4 analog to a degree similar to that of natural phylloquinone. Thus, the electron deficiency at the C-1' position is important for the conversion to MK-4.
在被人体利用之前，膳食维生素K同系物通过侧链部分的裂解和异戊烯基化反应转化为甲萘醌-4（MK-4）。我们预测异戊烯基化反应会因烯丙基部分C-1'位的电子缺乏而发生。因此，作为使C-1'位电子缺乏的另一种方法，通过引入酮基合成了一种新的维生素K衍生物，并研究了其向MK-4的转化。在已知难以转化为MK-4的2',3'-二氢叶绿醌侧链的C-1'位引入酮基，诱导其转化为MK-4类似物，转化程度与天然叶绿醌相似。因此，C-1'位的电子缺乏对于向MK-4的转化很重要。
